Detection of CrO4(2-) using a hydrogel swelling microcantilever sensor

Hydrogels containing various mounts of tetraalkylammonium salts were used to modify microcantilevers for measurements of the concentration of CrO4(2-) in aqueous solutions. These microcantilevers undergo bending deflection upon exposure to solutions containing various CrO4(2-) concentrations as a result of swelling or shrinking of the hydrogels. The microcantilever deflection as a function of the concentration of CrO4(2-) ions is nearly linear in most concentration ranges. It was found that a concentration of 10(-11) M CrO4(2-) can be detected using this technology in a fluid cell. Other ions, such as Br-, HPO4(2-), and NO3-, have minimal effect on the deflection of this cantilever. The anions SO4(2-) and CO3(2-) could interfere with the CrO4(2-) detection, but only at high concentrations (> 10(-5) M). Such hydrogel-coated microcantilevers could potentially be used to prepare microcantilever-based chemical and biological sensors when molecular recognition agents are immobilized in the hydrogel.     

Detection of Hg2+ using microcantilever sensors

Trace amounts of Hg2+ are detected by using a microcantilever coated with gold. The microcantilever undergoes bending due to accumulation of Hg2+ on the gold surface. It is found that a concentration of 10(-11) M Hg2+ can be detected using this technology. Other cations, such as K+, Na+, Pb2+, Zn2+, Ni2, Cd2+, Cu2+, and Ca2+ have little or no effect on the deflection of the cantilever. The selectivity of the Hg2+ sensor could be improved by coating the gold surface of microcantilever with a self-assembled monolayer of a long-chain thiol compound.     

Detection of femtomolar concentrations of HF Using an SiO(2) microcantilever

Femtomolar concentrations of hydrogen fluoride, a decomposition component of nerve agents, were detected using a SiO(2) microcantilever. The microcantilever underwent bending due to the reaction of HF with SiO(2). The microcantilever deflection increased as the concentration of HF increased. Other acids, such as HCl, had no effect on the deflection of the cantilever. The mechanism of reaction-induced bending and the correlation of microcantilever deflection with the HF concentration are discussed. The deflection in response to HF of a commercially available silicon cantilever was also studied, and its response was compared with that of the SiO(2) cantilever. Much less bending amplitude and sensitivity were observed for the silicon cantilever.     

Differentially ligand-functionalized microcantilever arrays for metal ion identification and sensing

A microcantilever array sensor with cantilevers differentially functionalized with self-assembled monolayers (SAMs) of thiolated ligands is prepared by simultaneous capillary coating. This array is described for the detection of metal ions including Li+, Cs+, Cu2+, Co2+, Fe3+, and Al3+. Binding of the charged metal cations to the surface of the microcantilever sensors produces surface stress that causes bending of the cantilevers that is detected as tip deflection using an array of vertical cavity surface emitting lasers and a position-sensitive detector. Optimization studies of the nanostructured dealloyed surface were performed for SAMs based on their response to Cu2+ cations. Sensor performance experiments demonstrate good sensitivity toward metal ions, with limits of detection as low as 10(-8) molar. A multiplex capillary coating method for cantilever array creation is demonstrated and validated based on surface-enhanced Raman spectra obtained from adjacent cantilevers that were functionalized with different thiolated SAMs. The cantilever array coated with a range of thiolated ligands was exposed to the group of metal ions. The response characteristics of each metal ion show substantial diversity, varying not only in response magnitude, but response kinetics. A pattern recognition algorithm based on a combination of independent component analysis and support vector machines was able to validate that the sensor array response profiles produced enough information content that metal ions could be reliably classified with probabilities as high as 89%.     

Glucose oxidase multilayer modified microcantilevers for glucose measurement

We report a novel enzyme-based microcantilever sensor by using layer-by-layer nanoassembly modification. A glucose oxidase (GOx) functionalized microcantilever underwent bending when it was exposed to glucose solutions. The magnitudes of bending were proportional to the concentrations of glucose. The cantilever bending was specific toward glucose, but not to other sugars such as mannose, fructose, or galactose. The flow rate effect on the cantilever bending response is also discussed. The bending mechanism was investigated, and the kinetic and thermodynamic analysis and experimental results showed that the conformational change of GOx and gluconic formation were the origin of cantilever deflection.     

Trace detection of peroxides using a microcantilever detector

A microcantilever sensor is reported for the trace detection of peroxide vapors. The sensor features a self-assembled monolayer that undergoes chain polymerization in the presence of peroxide radicals, causing a deflection of the cantilever. The generation of radicals using a heated filament, and the resulting surface polymerization reaction, is based on initiated Chemical Vapor Deposition chemistry. The sensor was successfully demonstrated with hydrogen peroxide and exhibited inherent reversibility and a selective, self-amplified response. Air and water were tested as interferents. This trace peroxide detector has industrial applications and addresses an aviation security need for the reliable detection of homemade explosives.     

Label-free detection of DNA hybridization based on hydration-induced tension in nucleic acid films

The properties of water at the nanoscale are crucial in many areas of biology, but the confinement of water molecules in sub-nanometre channels in biological systems has received relatively little attention. Advances in nanotechnology make it possible to explore the role played by water molecules in living systems, potentially leading to the development of ultrasensitive biosensors. Here we show that the adsorption of water by a self-assembled monolayer of single-stranded DNA on a silicon microcantilever can be detected by measuring how the tension in the monolayer changes as a result of hydration. Our approach relies on the microcantilever bending by an amount that depends on the tension in the monolayer. In particular, we find that the tension changes dramatically when the monolayer interacts with either complementary or single mismatched single-stranded DNA targets. Our results suggest that the tension is mainly governed by hydration forces in the channels between the DNA molecules and could lead to the development of a label-free DNA biosensor that can detect single mutations. The technique provides sensitivity in the femtomolar range that is at least two orders of magnitude better than that obtained previously with label-free nanomechanical biosensors and with label-dependent microarrays.     

Quantitative and label-free technique for measuring protease activity and inhibition using a microfluidic cantilever array

We report the use of a SiN x based gold coated microcantilever array to quantitatively measure the activity and inhibition of a model protease immobilized on its surface. Trypsin was covalently bound to the gold surface of the microcantilever using a synthetic spacer, and the remaining exposed silicon nitride surface was passivated with silanated polyethylene glycol. The nanoscale cantilever motions induced by trypsin during substrate turnover were quantitatively measured using an optical laser-deflection technique. These microcantilever deflections directly correlated with the degree of protease turnover of excess synthetic fibronectin substrate ( K M = 0.58 x 10 (-6) M). Inhibition of surface-immobilized trypsin by soybean trypsin inhibitor (SBTI) was also observed using this system.     

Influence of residual stress on diffusion-induced bending in bilayered microcantilever sensors

The influence of residual stress on diffusion-induced bending in bilayered microcantilever sensors has been analyzed under the framework of thermodynamic theory and Fick's second law. A self-consistent diffusion equation involving the coupling effects of residual stress and diffusion-induced stress is developed. Effects of thickness ratio, modulus ratio, diffusivity ratio and residual stress gradient of film and substrate on the curvature of bilayered cantilever are then discussed with the help of finite difference method. Results reveal that the curvature of bilayered cantilever increases with decreasing the diffusivity ratio and modulus ratio of substrate to film at a given time. Case study of the polysilicon/palladium hydrogen sensor has been finally carried out using the above developed bending theory.     

Nanomechanical detection of cholera toxin using microcantilevers functionalized with ganglioside nanodiscs

The label-free detection of cholera toxin is demonstrated using microcantilevers functionalized with ganglioside nanodiscs. The cholera toxin molecules bind specifically to the active membrane protein encased in nanodiscs, nanoscale lipid bilayers surrounded by an amphipathic protein belt, immobilized on the cantilever surface. The specific molecular binding results in cantilever deflection via the formation of a surface stress-induced bending moment. The nanomechanical cantilever response is quantitatively monitored by optical interference. The consistent and reproducible nanomechanical detection of cholera toxin in nanomolar range concentrations is demonstrated. The results validated with such a model system suggest that the combination of a microcantilever platform with receptor nanodiscs is a promising approach for monitoring invasive pathogens and other types of biomolecular detection relevant to drug discovery.     

Molecular interactions in self-assembly monolayers on gold-coated microcantilever electrodes

An electrochemical microcantilever (EMC) was used to study the intermolecular interaction of self-assembly monolayers (SAMs) with different n-alkanethiols chain lengths (n = 0, 4, 6, 8, 12, 16) on a Au-coated microcantilever surface. Comparing potential cycling and steps in NaClO(4) solution within the same potential range, the deflection rate of bare microcantilevers is much smaller for the former which revealed that potential excitation, i.e. the surface charge, played the dominant role in driving the instant and large deflection of the bare microcantilever, while the smaller deflection amplitude of the former implied that adsorption of ClO(4)( - ) had an adverse effect on the potential-induced stress. Upon adsorption of SAMs, the deflection amplitude of the microcantilever under the potential step was much smaller than that of a bare microcantilever, and linearly decreased with the chain length increasing for n ≤ 8 (the linear correlation coefficient and the slope are 0.98 and about - 10.4 nm per CH(2) unit, respectively), following a transition (8 ≤ n ≤ 12) to a stable state (n ≥ 12). The decrease of deflection amplitude and faster decay of deflection rate of the SAMs modified microcantilever under the potential step implyed increasing compactness of the SAMs with longer chains.     

X-ray fluorescence analysis of hexavalent chromium using Kβ satellite peak observed as counterpart of X-ray absorption near-edge structure pre-edge peak

A Kβ satellite peak in X-ray fluorescence (XRF) spectra is observed as a counterpart of the pre-edge peak of the X-ray absorption near edge structure (XANES). In Kβ emission of chromium, a small satellite peak is observed at 5.983-5.988 keV only for hexavalent chromium compounds such as CrO(3), Na(2)CrO(7)·2H(2)O, Na(2)CrO(4)·4H(2)O, K(2)Cr(2)O(7), K(2)CrO(4), Zn(2)CrO(4)(OH)(2)·2H(2)O, PbCrO(4), and BaCrO(4), together with the main peak at 5.947 keV, while trivalent chromium compounds such as Cr(2)O(3) and Cr(OH)(3)·nH(2)O show only the main peak at 5.947 keV. This corresponds to the fact that the K pre-edge peak in XANES is observed only for the hexavalent chromium compounds. The electronic level causing the satellite peak is almost at the same energy level as that causing the pre-edge peak. Our finding not only affects the interpretation of the origin of the pre-edge peaks but also leads to the simple speciation method of chromium compounds using XRF.     

Thionine covalently tethered to multilayer horseradish peroxidase in a self-assembled monolayer as an electron-transfer mediator

A new approach to construct a reagentless enzyme biosensor is described. Based on multilayer horseradish peroxidase in a self-assembled monolayer configuration, the biosensor was constructed using multilayer thionine covalently tethered to the enzyme as an electron-transfer mediator. The multilayer enzyme and the multilayer mediator were stepwisely synthesized onto an l-cysteine-assembled gold electrode using glutaraldehyde as a bifunctional reagent. The multilayer mediator tethered to the multilayer enzyme could effectively and stably shuttle electrons between the electrode and the multilayer enzyme linked onto the monolayer. The sensitivity of the resulting enzyme biosensor with eight layers of enzyme and three layers of mediator was more than 250 μA cm(-)(2) for 1.0 × 10(-)(4) mol/L hydrogen peroxide under optimal conditions, whereas such a modified electrode with one layer of enzyme and one layer of mediator did not yield a detectable response to 1.0 × 10(-)(4) mol/L hydrogen peroxide.     

Glucose biosensor based on the microcantilever

Diagnosis and management of diabetes require quantitative and selective detection of blood glucose levels. We report a technique for micromechanical detection of biologically relevant glucose concentrations by immobilization of glucose oxidase (GOx) onto a microcantilever surface. Microfabricated cantilevers have traditionally found utility in atomic force microscope imaging. During the past decade, however, microcantilevers have been increasingly used as transducers in chemical-sensing systems. This paper describes the combination of this technology with enzyme specificity to construct a highly selective glucose biosensor. The enzyme-functionalized microcantilever undergoes bending due to a change in surface stress induced by the reaction between glucose in solution and the GOx immobilized on the cantilever surface. Experiments were carried out under flow conditions. The common interferences for glucose detection in other detection schemes have been tested and have shown to have no effect on the measurement of blood glucose level by this technique.     

Low density lipoprotein sensor based on surface plasmon resonance

Biotinylated heparin has been immobilized onto self-assembled monolayer of 4-aminothiophenol using avidin–biotin specific binding. The modified electrodes have been characterized using surface plasmon resonance technique (SPR), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM) and contact angle (CA) measurements. The interaction of immobilized biotinylated heparin with low density lipoprotein (LDL) has been studied using surface plasmon resonance technique. The biotinylated heparin modified electrode can be used to detect LDL in the range of 20 to 100 mg/dl with the sensitivity of 513.3 m°/μM.     

Dielectric constants by multifrequency non-contact atomic force microscopy

We present a method to obtain capacitive forces and dielectric constants of ultra-thin films on metallic substrates using multifrequency non-contact atomic force microscopy with amplitude feedback in air. Capacitive forces are measured via cantilever oscillations induced at the second bending mode and dielectric constants are calculated by fitting an analytic expression for the capacitance (Casuso et al 2007 Appl. Phys. Lett. 91 063111) to the experimental data. Dielectric constants for self-assembled monolayers of thiol molecules on gold (2.0±0.1) and sputtered SiO2 (3.6±0.07) were obtained under dry conditions, in good agreement with previous measurements. The high Q-factor of the second bending mode of the cantilever increases the accuracy of the capacitive measurements while the low applied potentials minimize the likelihood of variation of the dielectric constants at high field strength and of damage from dielectric breakdown of air.     

Preparation of a self-assembled cytochrome c monolayer on a gold substrate for biomolecular device architecture

The segregation ability of 3-[(3-cholamidopropyl) dimethylammonio]-1-propanesulfonate (CHAPS), a zwitterionic surfactant, on cytochrome c (cyt c) aggregates in a phosphate buffer solution was quantified through the dynamic light-scattering analysis, and CHAPS was found to have an excellent ability in reducing nonspecific affinity among cyt c molecules. When CHAPS was applied to cyt c aggregates on the surface of gold substrates modified with self-assembled cyt c monolayer, the aggregates were found to be successfully eliminated by high-resolution atomic force microscopy image with 30-nm-sized cyt c clusters. This technique is expected to be useful to prepare a self-assembled monolayer of metalloproteins without their aggregates which may degrade the electrochemical property required as a biomolecular electronic device.     

Electrostatically actuated resonant microcantilever beam in CMOS technology for the detection of chemical weapons

The design, fabrication, and testing of a resonant cantilever beam in complementary metal-oxide semiconductor (CMOS) technology is presented in this paper. The resonant cantilever beam is a gas-sensing device capable of monitoring hazardous vapors and gases at trace concentrations. The new design of the cantilever beam described here includes interdigitated fingers for electrostatic actuation and a piezoresistive Wheatstone bridge design to read out the deflection signal. The reference resistors of the Wheatstone bridge are fabricated on auxiliary beams that are immediately adjacent to the actuated device. The whole device is fabricated using a 0.6-/spl mu/m, three-metal, double-poly CMOS process, combined with subsequent micromachining steps. A custom polymer layer is applied to the surface of the microcantilever beam to enhance its sorptivity to a chemical nerve agent. Exposing the sensor with the nerve agent simulant dimethylmethylphosphonate (DMMP), provided a demonstrated detection at a concentration of 20 ppb or 0.1 mg/m/sup 3/. These initial promising results were attained with a relatively simple design, fabricated in standard CMOS, which could offer an inexpensive option for mass production of a miniature chemical detector, which contains on chip electronics integrated to the cantilever beam.     

Solution chemistry approach to fabricate vertically aligned carbon nanotubes on gold wires: towards vertically integrated electronics

A monolayer of hexadecyltrichlorosilane, 3-aminopropyltriethoxysilane or 3-mercaptopropyltrimethoxysilane was self-assembled onto a p-type silicon (100) substrate to provide a resist for electrochemical anodization with an atomic force microscope cantilever. Silane treatment of the oxide nanostructures created by anodization lithography allowed for the creation of a chemically heterogeneous surface, containing regions of -NH(2) or -SH surrounded by -CH(3) functionality. These patterned regions of -NH(2) or -SH provided the point of attachment for citrate-stabilized gold colloid nanoparticles, which act as 'seed' particles for the electro-less deposition of gold. This has allowed the creation of gold wires on a silicon surface. Carbon nanotubes, with high carboxylic acid functionality, were vertically immobilized on the patterned gold wires with the use of a cysteamine monolayer and a condensation reaction. Such a material may prove useful in the creation of future vertically integrated electronic devices where it is desirable for electron transport to be in three dimensions and this electron transport is demonstrated with cyclic voltammetry.     

Corrosion and Fatigue Testing of Microsized 304 Stainless Steel Beams Fabricated by Femtosecond Laser

The 304 stainless steel (SS) microcantilever specimens with dimensions of 30 μm×30 μm×50μm (thickness×width × length) were fabricated by femtosecond (fs) laser. The microsized cantilevers of good quality with structure and dimensions according commendably with that of the designed cantilever were obtained. The result shows that fs laser micromachining is a promising method for directly fabricating metallic microcomponents.Corrosion and fatigue properties of microsized specimens were carried out on the microsized 304 SS cantilever beams by a newly developed fatigue testing machine. The results show that the microsized 304 SS specimens appear to have an improved resistance towards localized corrosion compared to ordinary-sized 304 SS specimens after the static corrosion testing. The testing result shows that the presence of corrosive solution reduces the fatigue lifetime of the 304 SS specimen by a factor of 10-100. The maximum bending loads measured by fatigue testing machine decrease rapidly at the terminal stage of environment assisted fatigue testing.Corrosion fracture first occurred at the range of notch with a higher tensile bending stress, and exhibited clear evidence of trans-columnar fracture detected by SEM (scanning electron microscopy).