US20060057026A1 - Gold thiolate and photochemically functionalized microcantilevers using molecular recognition agents - Google Patents

Gold thiolate and photochemically functionalized microcantilevers using molecular recognition agents Download PDF

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US20060057026A1
US20060057026A1 US11/152,627 US15262705A US2006057026A1 US 20060057026 A1 US20060057026 A1 US 20060057026A1 US 15262705 A US15262705 A US 15262705A US 2006057026 A1 US2006057026 A1 US 2006057026A1
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functionalized
coating
rinsing
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chromate
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Vassil Boiadjiev
Gilbert Brown
Lal Pinnaduwage
Thomas Thundat
Peter Bonnesen
Gudrun Goretzki
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UT Battelle LLC
University of Tennessee Research Foundation
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Priority to EP05809927A priority patent/EP1794580A2/de
Priority to PCT/US2005/032877 priority patent/WO2007011376A2/en
Priority to PCT/US2005/032637 priority patent/WO2006031846A2/en
Priority to EP05858414A priority patent/EP1815236A2/de
Priority to US11/662,696 priority patent/US20080206103A1/en
Priority to CA002580593A priority patent/CA2580593A1/en
Priority to CA002580599A priority patent/CA2580599A1/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
    • G01N29/02—Analysing fluids
    • G01N29/022—Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y35/00—Methods or apparatus for measurement or analysis of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/025—Change of phase or condition
    • G01N2291/0256—Adsorption, desorption, surface mass change, e.g. on biosensors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/04—Wave modes and trajectories
    • G01N2291/042—Wave modes
    • G01N2291/0423—Surface waves, e.g. Rayleigh waves, Love waves
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/04—Wave modes and trajectories
    • G01N2291/042—Wave modes
    • G01N2291/0426—Bulk waves, e.g. quartz crystal microbalance, torsional waves
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/04—Wave modes and trajectories
    • G01N2291/042—Wave modes
    • G01N2291/0427—Flexural waves, plate waves, e.g. Lamb waves, tuning fork, cantilever

Definitions

  • 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.
  • MEMS microelectromechanical systems
  • SAM self-assembled monolayers
  • 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.
  • the microcantilevers 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.
  • Micro-electro-mechanical systems are likely candidates for extremely sensitive, inexpensive sensors, which can be mass produced.
  • Microcantilever sensors offer much better sensitivities compared to other MEMS sensors and have surface areas of the order 10 ⁇ 4 cm 2 , which is smaller than that of other miniature devices (such as Surface Acoustic Wave devices, SAW) by orders of magnitude. They can be mass produced at relatively low cost using standard semiconductor manufacturing processes and have demonstrated superior detection sensitivities for physical, chemical and biological sensing.
  • 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.
  • Chemical selectivity has been achieved by coating the gold surface of the microcantilevers with a selective film such as a self-assembled monolayer (SAM) of an alkane thiol having a head group suitable for molecular recognition.
  • a selective film such as a self-assembled monolayer (SAM) of an alkane thiol having a head group suitable for molecular recognition.
  • functionalized films can be attached to hydrogen terminated silicon and silicon nitride surfaces by photochemical hydrosilylation to achieve more stable coatings.
  • the main feature distinguishing microcantilevers from other MEMS is their unique bending response. 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.
  • This bending detection mode can be used in liquid phase, as well as in gas phase, which makes cantilever sensors suitable for both molecular and ionic analytes if selective adsorption can be achieved on one of their surfaces using analyte-specific surface functionalities.
  • a preferred approach to the design of selective sensors is to immobilize agents for selective molecular recognition in a matrix that mimics the organic medium in a solvent extraction system. In this manner, the matrix can enhance both the separation and the achievement of chemical selectivity.
  • the transduction part of the microcantilever sensor is based on binding the molecular recognition agent to one surface of the cantilever so that the adsorption-induced stress change can be detected via bending of the microcantilever.
  • 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.
  • the photoactivation method of this invention provides a solution to this problem wherein cantilevers are only activated to react with an ethylene substituted hydrocarbon when irradiated with UV light.
  • Arrays of cantilevers can be conveniently prepared with each cantilever or group of cantilevers having a separate molecular recognition agent to impart chemical selectivity. Attachment of molecular recognition agents to the surface with robust Si—C bonds gives a layer with superior stability. For example, chromium(VI) or chromate can be selectively detected by the microcantilever of this invention.
  • Chromium is naturally occurring in several different oxidation states. The most frequently encountered forms are the III and VI oxidation states. Chromium(III) is an essential trace element in the human body and plays an important role in the metabolism of glucose, lipids, and proteins. In contrast, Cr(VI) in the form of chromate (CrO 4 2 ⁇ ) is considered to be toxic to animals and humans. Most of the methods used to determine CrO 4 2 ⁇ (such as ion exchange, chromatography, and atomic absorption spectroscopy) are generally time-consuming, have less than desired accuracy, or are expensive.
  • Cr(VI) is more soluble in groundwater than Cr(III), and thus has a greater potential of affecting human health and the environment.
  • 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.
  • the method that is widely being used at present requires selective reaction of Cr(VI) with 1,5-diphenylcarbohydrazide followed by spectrophotometry.
  • the commercial sensor technique based on the above method and used widely for Cr(VI) monitoring has a detection limit of ⁇ 1.9 ⁇ 10 ⁇ 7 M, close to the current EPA regulation level of 2.1 ⁇ 10 ⁇ 7 M.
  • MEMS microelectromechanical systems
  • 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.
  • One embodiment of the device and method enables the detection of hexavalent chromium, Cr(VI), in ground water using a single microcantilever sensor coated with a self-assembled monolayer of 4-mercaptopyridine.
  • CrO 4 2 ⁇ ions can be detected with the microcantilever sensor in the presence of significant concentrations (>1000 pg/l) of Ca 2+ , Cl ⁇ , Mg 2+, NO 3 ⁇ , K + , Na + , and SO 4 2 ⁇ ions and a variety of other ions of smaller concentrations.
  • the chromate concentrations were also measured using the Hach spectrophotometric kit, which is widely used for chromate monitoring.
  • the cantilever measurements are an order of magnitude more sensitive compared to the spectrophotometric method currently in use, and are amenable for remote detection.
  • the microcantilever sensor uses gold-thiol or photochemical hydrosilylation to modify the microcantilever surface.
  • the photochemical process enables individual microcantilevers in multicantilever array chips to be modified separately by focusing the activating UV light sequentially on each particular cantilever. Grafting of selected gold coated microcantilevers can be achieved by spotting techniques.
  • the surface functionalities retain their affinity toward Cr(VI), and the organic monolayer is dense enough to generate significant surface stress upon subsequent adsorption of chromate ions from aqueous solutions.
  • FIGS. 1 a and 1 b are graphs showing (a) Results of the photometric measurements on the three water samples from the Hanford site. (b) Comparison of the photometric signal from the B173R9 sample with those from standard chromate solutions of concentrations of 2.5 ⁇ 10 ⁇ 7 M and 5.0 ⁇ 10 ⁇ 7 M.
  • FIGS. 2 a and 2 b are graphs showing cantilever bending signals of 4-Mpy modified cantilever due to the injections of different amounts of the acidified sample solutions at 10 mL/hr; (a) different amounts of B173R7 and (b) same amount of B173R8 samples.
  • the relative magnitudes of the cantilever bending signals (after normalizing to the injection volumes) are in agreement with the relative concentrations obtained from the photometric measurements.
  • FIG. 3 is a graph showing cantilever bending signal due to the injection of 2 mL (at pumping speed of 10 mL/hr) of the acidified B173R9 water sample taken from a well at the Hanford site. From historical data for this well, the concentration of hexavalent chromium is expected to be ⁇ 2.5 ⁇ 10 ⁇ 7 M. The water from this well contains numerous other contaminants, some of which have concentrations exceeding 10 ⁇ 4 M.
  • FIG. 4 is the bending response of a gold-coated silicon microcantilever, modified with 11-undecenyltriethylammonium bromide by photochemical hydrosilylation on the silicon side, upon injections of 1 mL of sample chromate solutions: (1) 1 ⁇ 10 ⁇ 4 M CrO 4 2 ⁇ , left scale; (2) 1 ⁇ 10 ⁇ 9 M CrO 4 2 ⁇ , right scale.
  • FIG. 5 shows photochemical hydrosilylation of alkenes and alkynes. Figure taken from Buriak, Chem. Rev. 2002, 102 (5), 1271-1308.
  • FIG. 6 shows surface structures reported by Buriak, Chem. Rev. 2002, 102 (5), 1271-1308 and Voicu, R., Langmuir, 2004, 20, pp. 11713-11720.
  • FIG. 7 shows anticipated structure of Si surface modified with quaternary ammonium coating and bonding mode for chromate. It is a schematic representation of a cantilever Si surface functionalized with 11-undecenyltriethylammonium halide using the photochemical hydrosilylation approach for chromate detection. X— ⁇ Br— immediately following the hydrosilylation process.
  • FIG. 8 shows photochemical hydrosilylation of 11-undecenyltriethylammonium bromide to hydrogen terminated microcantilevers.
  • FIG. 9 is a photograph of a typical functionalized microcantilever.
  • Chromate cantilever sensors using two different types of chromate-specific surface functionalities bound to gold-coated cantilever surfaces as thiol-based pyridine and thiol-based quaternary ammonium terminated self-assembled monolayers (SAMs) are described.
  • the 4-mercaptopyridine based microcantilever chromate sensor has exceptional stability and very high selectivity and can be used for months in acidic media utilizing a single cantilever.
  • Ethanol solutions of the quaternary ammonium terminated thiol ( ⁇ 1 mM) from the self-assembly process were studied 2 weeks after the cantilever treatment and indicated significant degradation of the quaternary ammonium thiol. Some decomposition was also detected in the solid compound, which was stored in a closed container for a similar time period. We hypothesize that nucleophilic attack of the sulfur on the carbon attached directly to the positive nitrogen analogous to Hofmann degradation may have occurred.
  • Photochemical Hydrosilylation Direct covalent attachment of the quaternary ammonium monolayer via robust Si—C bonds ( FIG. 4 ) improved the stability and robustness of the cantilever sensors. This is achieved in a two-step process involving hydrogen termination of the silicon cantilever surface and subsequent photochemical (UV) hydrosilylation with the unsaturated hydrocarbon chain of the quaternary ammonium compound, which results in a stable Si—C surface linkage ( FIG. 8 ).
  • Anhydrous methylene chloride (Aldrich Chemical Co., 99.8%, bottled under nitrogen) was additionally dried with CaH 2 , degassed by at least six freeze-pump-thaw cycles, and then distilled under vacuum into the cooled quartz cell compartment containing the 11-undecenyltriethylammonium bromide. Upon reaching room temperature, the quartz cell was backfilled with high-purity argon and a clear solution with an approximate concentration between 0.1 and 0.15 M was prepared under magnetic stirring. This solution was then carefully poured into the other cell compartment containing the hydrogen-terminated silicon microcantilevers.
  • the argon-filled quartz cell was closed, disconnected from the vacuum manifold, and then placed into a bigger quartz vessel containing water to prevent heating during UV irradiation.
  • the silicon surface was irradiated using frequencies emitted by a mercury lamp (100 W, ⁇ 25 cm distance from the surface) for 7-10 days to ensure sufficient time for dense packing of the positively charged quaternary ammonium terminated hydrocarbon chains. This time scale was prompted from our earlier results in the case of the self-assembly of mercapto-terminated quaternary ammonium hydrocarbon chains on gold-coated microcantilever surfaces, which needed about 1 week to yield the desired sensitivity to chromate ions.
  • Cantilever deflection measurements were conducted in the optical mode using an atomic force microscopy (AFM) head. The experiments were performed in a flow-through glass fluid cell that holds the V-shaped microcantilever. The volume of the flow cell was 0.3 cm 3 , ensuring fast replacement of the solution.
  • a constant flow rate of 10 ml/h for the ultrapure (or tap) water carrier was maintained using a syringe pump.
  • Samples of chromate solutions were introduced by directing the carrier through a 1-mL reservoir HPLC loop using a switch valve. This provided about 6 min contact time of the analyte with the active cantilever surface.
  • the bending of the cantilever was measured by monitoring the position of a laser beam reflected off the apex of the cantilever (from the gold-coated surface) onto a position sensitive detector.
  • Another advantage of the stable quaternary ammonium cantilever sensor is its ability to detect chromate ions directly in liquid, neutral aqueous solutions, vapor, and gas, thus potentially eliminating the necessity for sample collection and preparation (such as acidifying to pH 1 in the case of the 4-mercaptopyridine based sensor).
  • Such a chromate sensor that incorporates a reference cantilever (inert toward Cr(VI), for example, a clean Au-coated silicon cantilever) in a multicantilever array may be suitable for direct monitoring of groundwater and industrial wastewater.
  • Using reference cantilever(s) in a multicantilever array can reduce adverse environmental effects such as gross changes in ionic strength and thermal drifts. Further optimization of this photochemical surface functionalization process may allow even better chromate sensitivity and selectivity with the desired stability and robustness necessary for field applications.
  • Another embodiment of this invention is a method of modifying the surface of individual cantilevers in an array so that each cantilever (or a group of cantilevers) can have separate selectivity for sorption of analytes of interest.
  • the chemical modification involves the formation of robust Si—C bonds that are more chemically resistant than Si—O—Si bonding or the thiol SAMs on a gold coated microcantilever.
  • Silicon microcantilevers having gold on one side are treated with NH 4 F to form Si—H terminated surface on the uncoated silicon side of the cantilever. This Si—H surface can be photochemically activated with UV light to react with an olefin.
  • the olefin will not react with the Si—H bonds at room temperature, thus an array of cantilevers under a solution containing an olefin will not react until irradiated with UV light.
  • the solution can be removed from the array of cantilevers, rinsed with a suitable solvent, and a second olefin functionalized with another molecular recognition end group can be added and induced to react with UV irradiation. This process can be repeated as often as necessary to create an array of cantilever sensors with different functionalities.
  • This chemistry is compatible with a variety of molecular recognition agents including quaternary ammonium and pyridine groups (chromate selective), crown ethers and azacrown compounds (metal ion selective), borate esters (sugars), ureas (nitrate and organonitrate compounds), biomolecule-selective antibody-antigens, DNA, proteins, as well as organic acids, esters, amides, amines, aldehydes, phosphonic acids and esters, and related compounds.
  • molecular recognition agents including quaternary ammonium and pyridine groups (chromate selective), crown ethers and azacrown compounds (metal ion selective), borate esters (sugars), ureas (nitrate and organonitrate compounds), biomolecule-selective antibody-antigens, DNA, proteins, as well as organic acids, esters, amides, amines, aldehydes, phosphonic acids and esters, and related compounds.
  • UV irradiation can promote hydrosilylation of unsaturated compounds due to homolytic cleavage of Si—H bonds
  • UV photoinduction takes place at room temperature and thus provides a way to avoid problems from thermal input that could be harmful to delicate or small features on a silicon chip. Minimal input of thermal energy would be preferable in any IC manufacturing process (thermal budget).
  • the cantilever deflection measurements were conducted in the optical mode using an Atomic Force Microscopy (AFM) head.
  • the cantilever bending signal (which depends on the cantilever dimensions as well as on the electronic circuit details) was converted to a surface stress in order to express in universal terms.
  • the experiments were performed in a flow-through glass fluid cell that holds the V-shaped microcantilever (180 ⁇ m long, 1 ⁇ m thick, and a force constant of 0.26 N/m) from Thermomicroscopes, CA.
  • the manufacturer had coated one side of these cantilevers with gold (a 30-nm thick gold layer on top of a 3-nm titanium adhesion layer).
  • the metallic coating can be at least one of Au, Pt, Cu, Pd, Al, or Ti.
  • the volume of the glass cell was 0.3 cm 3 , ensuring fast replacement of the solution.
  • a constant flow rate of 10 ml/hr for the acidic carrier solution (0.1 N H 2 SO 4 in ultrahigh purity deionized water, pH 1) was used in these experiments; ground water samples or standard chromium (VI) solutions acidified the same way were injected into the carrier.
  • the B—B stacking between the aromatic 4-mercaptopyridine (4-MPy) molecules and their conformational rigidity within the SAM have the tendency to align them into polymer-like chains, which can be observed by scanning tunneling microscopy (STM).
  • Gold-coated silicon cantilevers were cleaned in acetone, in absolute ethanol, in deionized water, and (for only 10 s) in piranha solution (7:3 H 2 SO 4 98%/H 2 O 2 31%), and rinsed with ultrapure deionized water (3 times) and absolute ethanol (2 times).
  • the formation of a 4-MPy SAM on the gold surface of the cantilever was achieved by immersing the cantilever into an acidic aqueous solution of 5 ⁇ 10 ⁇ 3 M of 4-MPy (95%, from Aldrich Chemical Company) in 0.1 NH 2 SO 4 /de-ionized water for six days. Upon removal from the solution, the cantilever was rinsed with de-ionized water and then dried before use in the experiments.
  • FIG. 1 a shows the photometric data for the 3 samples.
  • the chromate concentration in the B173R9 sample is below the detection level of the photometric method, and samples B173R8 and B173R7 have chromate concentrations of ⁇ 2.4 ⁇ 10 ⁇ 6 M and ⁇ 3.7 ⁇ 10 ⁇ 5 M, respectively. These numbers agree reasonably well with the historical data for these wells.
  • the cantilever bending response from acidified ground water samples B173R7 and B173R8 are shown in FIG. 2 .
  • the bending signal is roughly proportional to the amount of the sample injected; on the other hand, similar bending signals are obtained when the same amount of chromate is injected; see FIG. 2 ( b ).
  • the signal level for the B173R8 sample is roughly 10 times smaller compared to that of the B173R7 sample when normalized to the injection volumes.
  • the cantilever bending data are in agreement with the photometric data for those two samples. In the data of FIG. 2 the cantilever bending is only partially recovered after the exposure to chromate.
  • Partially reversible chromate signals may be due to two-step surface process involving rapid reversible displacement of sulphate in the vicinity of the positively charged (protonated) 4-mercaptopyridinium layer for chromate (lower hydration energy), followed by stronger and much less reversible complexation, of chromate to the SAM surface.
  • fast (minutes) ion exchange in the diffuse ionic layer may be responsible for the fast initial recovery followed by much slower (hours) desorption of the strongly bound chromate.
  • the negative value of the Frumkin parameter for the chromate-pyridinium interaction indicates a repulsive force between the adsorbed chromate ions, which becomes very significant at high surface concentrations.
  • These repulsive chromate-chromate interactions may be responsible for the extremely large cantilever bending signals (>1 N/m) at high chromate surface coverage, reflecting a huge increase of the adsorption-induced surface stress.
  • the cantilever sensitivity significantly increased after a “critical” surface concentration of pre-adsorbed chromate was achieved by injection of standard chromate solution. (following the electrochemical recovery).
  • the remaining chromate species will have a low enough surface density, which assures minimal chromate-chromate electrostatic repulsion.
  • the sensor is than ready to respond with a strong signal to any, even minimal, change in the surface stress induced by adsorbing any chromate ions in closer than this equilibrium proximity.
  • the mobile nature of any hydrogen-bonding interaction leads to the removal of pre-adsorbed chromate species by the clean acidified water carrier.
  • Cantilever response to the acidified B173R9 sample shows that the cantilever is able to detect this low chromate level clearly. Comparing this signal magnitude with cantilever data for the B173R7 sample ( FIG. 2 ( a )) and the B173R8 sample ( FIG. 2 ( b )) yielded estimated concentrations of 1 ⁇ 10 ⁇ 7 M and 6 ⁇ 10 ⁇ 8 M respectively for the B173R9 sample. Therefore, we estimate the concentration of the B173R9 sample to be ⁇ 8 ⁇ 10 ⁇ 8 M. At lower chromate concentrations, much larger sample volumes are used at the same pumping speed, thus also increasing the contact time between the chromate and the pyridinium layer.
  • An estimate of the detection threshold can be obtained by using the data of FIG. 3 , and estimating the chromate concentration that would be above the noise level of FIG. 3 .
  • the noise level By taking the noise level to be 3 standard deviations of the background fluctuations (i.e. ⁇ 3 ⁇ 0.002 N/m), we obtained a detection threshold of 4 ⁇ 10 ⁇ 9 M.
  • the detection threshold is roughly an order of magnitude better than the photometric method.
  • Cicero R. L.; Linford, M. R.; Chidsey, C. E. D. Langmuir, 2000, 16, 5688.
  • alkenes and alkynes were successfully tried, including 1-octene, 1-octadecene, 1-octyne, styrene, and phenylacetylene, with the alkenes yielding alkyl monolayers and the alkynes yielding alkenyl monolayers. Examples of surfaces prepared and discussed in the literature are shown in FIG. 6 .
  • the mechanism proposed is radical based, with homolytic Si—H bond cleavage initiating the reaction to form a silicon radical (dangling bond). Because silicon radicals are known to react very rapidly with unsaturated carbon-carbon bonds, Si—C bond formation is expected to be a facile step, forming the surface-bound carbon-based radical on the ⁇ -carbon of the olefin. Abstraction of neighboring hydrogen completes the hydrosilylation. On the basis of the bond strengths of the weakest Si—H bond on a silicon surface, the monohydride Si—H group ( ⁇ 3.5 eV), it appears that a minimum of 3.5 eV UV ( ⁇ 350 nm) is required to efficiently perform Si—H bond homolysis.
  • the photochemical surface activation strategy can also allow individual cantilevers in multicantilever array chips to be modified separately by focusing the activating UV light sequentially on each particular cantilever.
  • a set of reactant solutions can be prepared and recycled in a sequential photochemical treatment procedure where the array will be exposed to one solution at a time. The entire chip would be washed with solvent following each UV irradiation before the next solution is brought in. This will allow specific modification of individual irradiated cantilevers on the chip, which cannot be achieved using non-selective thermal activation.
  • Thermal activation would initiate deposition of the same organic layer on all cantilever surfaces at the same time.
  • carrying out the photochemical reaction at ambient temperature eliminates cantilever deformations due to bimetallic effects upon heating. Increasing the number of independently functionalized cantilevers on an array chip would strongly enhance the recognition power of the sensor device.
  • Such modified surfaces can also be used as reactive platforms for further surface functionalization by spotting.
  • the Ti/Au coating of the cantilevers did not appear to interfere with the photochemical silicon functionalization process when a 40% NH4F solution was used to produce the hydrogen-terminated silicon surface. It was severely attacked when an HF treatment was attempted. Nevertheless, a protective Ti/Au coating may not be required if only one side of the lever can be selectively modified during the photochemical hydrosilylation step, while the other hydrogen-terminated silicon side will oxidize back to its original functionality upon contact with water and air following the photochemical process.
  • Photochemical hydrosilylation of silicon cantilevers is, suitable for cantilever sensor development if the desired surface functionality is compatible with the reaction requirements.
  • the resulting functionalized organic layers can be dense enough to generate sufficient surface stress upon specific analyte adsorption at low concentrations.
  • Cantilever sensors prepared using these strategies have unsurpassed robustness and stability due to the direct covalent Si—C linkage.
  • Chemical selectivity can be achieved by arrays consisting of several microcantilevers, each coated with different selective or partially selective coatings.
  • the response of a given modified microcantilever will depend on the concentration of the analyte and the strength of the coating-analyte interactions (e.g. hydrogen bonding, dispersion, and dipole-dipole interactions).
  • a unique response pattern characteristic to a particular analyte can be obtained from an array where each microcantilever is modified with a different coating. The higher the number of modified cantilevers, the greater the uniqueness of the response pattern.
  • microcantilever response to a given analyte depends on the functional end-groups of modifying agents, judicious selection of coatings can lead to significant differences in the response patterns for different analytes.
  • array consisting of a large number of microcantilevers unique response patterns can be attained for individual analytes, class of analytes, or analytes in complex mixtures. The results of testing with a large number of analyte and mixtures are recorded in a look-up table and referenced routinely when an array is in service.
  • hydrosilylation procedure which in certain cases can be combined with sequential surface reactions, it is possible to derive coatings containing various molecular recognition groups such as hydrocarbon chains, esters, metal-containing organic functionalities, buckyballs (C-60), carboxylic acids, and even hydroxyls.
  • various molecular recognition groups such as hydrocarbon chains, esters, metal-containing organic functionalities, buckyballs (C-60), carboxylic acids, and even hydroxyls.
  • hydrocarbon layers grafted directly on the silicon surface for gasoline detection FIG. 6 .
  • Environmental sampling and process control are areas wherein the arrays offer advantages of size, simplicity and reliability.

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US11/152,627 US20060057026A1 (en) 2004-09-14 2005-06-14 Gold thiolate and photochemically functionalized microcantilevers using molecular recognition agents
CA002580599A CA2580599A1 (en) 2004-09-14 2005-09-14 Gold thiolate and photochemically functionalized microcantilevers using molecular recognition agents
CA002580593A CA2580593A1 (en) 2004-09-14 2005-09-14 Self-assembled monolayers on the surface of gold coated microcantilevers for application to chemical sensing and method of operation
US11/662,696 US20080206103A1 (en) 2004-09-14 2005-09-14 Method For The Preparation Of Very Stable, Self-Assembled Monolayers On The Surface Of Gold Coated Microcantilevers For Application To Chemical Sensing
EP05858414A EP1815236A2 (de) 2004-09-14 2005-09-14 Goldthiolat und fotochemisch funktionalisierte miktorkantilever mit molekularen erkennungsmitteln
PCT/US2005/032877 WO2007011376A2 (en) 2004-09-14 2005-09-14 Gold thiolate and photochemically functionalized microcantilevers
PCT/US2005/032637 WO2006031846A2 (en) 2004-09-14 2005-09-14 Self-assembled monolayers on the surface of gold coated microcantilevers for application to chemical sensing and method of operation
EP05809927A EP1794580A2 (de) 2004-09-14 2005-09-14 Selbstmontierende monoschichten auf der oberfläche von goldbeschichteten mikrokantilevern zur anwendung bei der chemischen abtastung und herstellungsverfahren dafür
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US20080085379A1 (en) 2008-04-10
EP1815236A2 (de) 2007-08-08
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