Gold Surface Of Quartz Crystal Microbalance Research Articles

Electro-Responsive Surface Composition and Kinetics of an Ionic Liquid in a Polar Oil.

The quartz crystal microbalance (QCM) has been used to study how the interfacial layer of an ionic liquid dissolved in a polar oil at low weight percentages responds to changes in applied potential. The changes in surface composition at the QCM gold surface depend on both the magnitude and sign of the applied potential. The time-resolved response indicates that the relaxation kinetics are limited by the diffusion of ions in the interfacial region and not in the bulk, since there is no concentration dependence. The measured mass changes cannot be explained only in terms of simple ion exchange; the relative molecular volumes of the ions and the density changes in response to ion exclusion must be considered. The relaxation behavior of the potential between the electrodes upon disconnecting the applied potential is more complex than that observed for pure ionic liquids, but a measure of the surface charge can be extracted from the exponential decay when the rapid initial potential drop is accounted for. The adsorbed film at the gold surface consists predominantly of ionic liquid despite the low concentration, which is unsurprising given the surtactant-like structures of (some of) the ionic liquid ions. Changes in response to potential correspond to changes in the relative numbers of cations and anions, rather than a change in the oil composition. No evidence for an electric field induced change in viscosity is observed. This work shows conclusively that electric potentials can be used to control the surface composition, even in an oil-based system, and paves the way for other ion solvent studies.

Effective antibodies immobilization and functionalized nanoparticles in a quartz-crystal microbalance-based immunosensor for the detection of parathion.

BackgroundBiosensor-based detection provides a rapid and low-cost alternative to conventional analytical methods for revealing the presence of the contaminants in water as well as solid matrices. Although important to be detected, small analytes (few hundreds of Daltons) are an issue in biosensing since the signal they induce in the transducer, and specifically in a Quartz-Crystal Microbalance, is undetectable. A pesticide like parathion (M = 292 Da) is a typical example of contaminant for which a signal amplification procedure is desirable.Methods/FindingsThe ballasting of the analyte by gold nanoparticles has been already applied to heavy target as proteins or bacteria to improve the limit of detection. In this paper, we extend the application of such a method to small analytes by showing that once the working surface of a Quartz-Crystal Microbalance (QCM) has been properly functionalized, a limit of detection lower than 1 ppb is reached for parathion. The effective surface functionalization is achieved by immobilizing antibodies upright oriented on the QCM gold surface by a simple photochemical technique (Photonic Immobilization Technique, PIT) based on the UV irradiation of the antibodies, whereas a simple protocol provided by the manufacturer is applied to functionalize the gold nanoparticles. Thus, in a non-competitive approach, the small analyte is made detectable by weighing it down through a “sandwich protocol” with a second antibody tethered to heavy gold nanoparticles. The immunosensor has been proved to be effective against the parathion while showing no cross reaction when a mixture of compounds very similar to parathion is analyzed.Conclusion/SignificanceThe immunosensor described in this paper can be easily applied to any small molecule for which polyclonal antibodies are available since both the functionalization procedure of the QCM probe surface and gold nanoparticle can be applied to any IgG, thereby making our device of general application in terms of target analyte.

Strategy to design DNA-biosensors: Single-stranded probe grafting versus target–probe duplex grafting

A strategy to design DNA-biosensors by grafting probe–target duplex onto a 27 MHz quartz crystal microbalance gold surface is presented in this work. The idea that removing the DNA target after duplex grafting yields to a well accessible probe, and therefore to efficient target recognition, is investigated. Unfortunately, hybridization efficiency measured using such a straightaway protocol is equal to 15%, which is feeble by comparison with the 31% hybridization efficiency measured for biosensors designed with single-stranded probe. Successive DNA biosensors are designed in this work, taking into account phenomena that occur specifically in an interfacial environment, like non specific adsorption or exchange reactions between adsorbed molecules. A DNA-biosensor with an optimized biolayer in terms of probe accessibility and probe surface density is in fine designed: a 59% hybridization efficiency, for a complementary target including a 20-base non complementary sequence oriented toward the surface, is obtained for the biosensor designed with target–probe duplex. This hybridization efficiency is 3 times to 18% measured for biosensors designed with single-stranded probe.

Diagnosis and genotyping of Plasmodium falciparum by a DNA biosensor based on quartz crystal microbalance (QCM)

Malaria infection with Plasmodium falciparum is an important basic health problem in the tropical and sub-tropical countries. The standard diagnostic method is blood film examination to visualize parasite morphology. However, in cases of low parasitemia or mixed infection with very low cryptic species, microscopy is not sensitive enough. Therefore, molecular techniques have been widely employed. A label-free DNA biosensor based on quartz crystal microbalance (QCM) to diagnose and genotype P. falciparum was developed. Avidin-biotin interaction was used to coat the specific biotinylated probe on the gold surface of QCM. The gene encoding merozoite surface protein 2 (msp2) was amplified and the PCR products were then cut with restriction enzyme (MwoI). Enzymatic cutting made the PCR products suitable for QCM development. Hybridization between probe and enzymatic cutting DNA fragments resulted in frequency changes of the QCM. The newly developed QCM was tested for its diagnosis ability using both malaria laboratory strains and clinical isolates. The biosensor was sensitive at the sub-nanogram level, specific for only P. falciparum detection, no cross-reaction with P. vivax, and stable at room temperature for up to 6 months. Selection of msp2 as a target gene and a geno-typing marker made the QCM potentially useful for falciparum diagnosis simultaneously with genotyping. Potency was tested by genotyping two allelic families of P. falciparum, FC27 and IC1, using malaria laboratory strains, K1 and 3D7, respectively. The dual function QCM was successfully developed with high sensitivity and specificity, and was cost-effective, stable and field adaptable.

Method for detection of Hg2+ based on the specific thymine–Hg2+–thymine interaction in the DNA hybridization on the surface of quartz crystal microbalance

A simple and sensitive method was developed for the detection of mercury ions with quartz crystal microbalance (QCM), based on the specific thymine-Hg(2+)-thymine (T-Hg(2+)-T) interaction and gold nanoparticle-mediated signal amplification. To enhance the sensitivity of detection a sandwich hybridization approach was adopted in this work. The QCM gold surface was modified with the probe SH-oligonucleotides (Oligo-1) and 6-Mercapto-1-hexanol to form an active surface for the hybridization of a longer ss-DNA (Oligo-2), and then Oligo-3 hybridazated with an excess and matching part of Oligo-2. In all oligonucleotides, there existed T bases. In the presence of Hg(2+) ions, special T-Hg(2+)-T reaction greatly enhanced the hybridization of oligonucleotides and detection sensitivity. The gold nanoparticle (Au NPs) amplifier method further increased the sensitivity of detection. A detection sensitivity of 5nM Hg(2+) was obtained in the QCM system, whereas other coexisting metal ions (such as Ni(2+), Mg(2+), Co(2+), Cr(3+), Pb(2+), Cd(2+), Mn(2+), Ba(2+)) had no significant interference. This method reveals a new approach for the manufacture of a kind of simple and low cost sensors for the Hg(2+) detection.

DNA probe functionalized QCM biosensor based on gold nanoparticle amplification for Bacillus anthracis detection

The rapid detection of Bacillus anthracis, the causative agent of anthrax disease, has gained much attention since the anthrax spore bioterrorism attacks in the United States in 2001. In this work, a DNA probe functionalized quartz crystal microbalance (QCM) biosensor was developed to detect B. anthracis based on the recognition of its specific DNA sequences, i.e., the 168 bp fragment of the Ba813 gene in chromosomes and the 340 bp fragment of the pag gene in plasmid pXO1. A thiol DNA probe was immobilized onto the QCM gold surface through self-assembly via Au–S bond formation to hybridize with the target ss-DNA sequence obtained by asymmetric PCR. Hybridization between the target DNA and the DNA probe resulted in an increase in mass and a decrease in the resonance frequency of the QCM biosensor. Moreover, to amplify the signal, a thiol-DNA fragment complementary to the other end of the target DNA was functionalized with gold nanoparticles. The results indicate that the DNA probe functionalized QCM biosensor could specifically recognize the target DNA fragment of B. anthracis from that of its closest species, such as Bacillus thuringiensis, and that the limit of detection (LOD) reached 3.5 × 10 2 CFU/ml of B. anthracis vegetative cells just after asymmetric PCR amplification, but without culture enrichment. The DNA probe functionalized QCM biosensor demonstrated stable, pollution-free, real-time sensing, and could find application in the rapid detection of B. anthracis.

Antibody Immobilization on Functional Monolayers Using a Quartz Crystal Microbalance

This paper evaluated immobilization of anti-C-reactive protein (CRP) monoclonal antibody on a quartz crystal microbalance (QCM) when 2-aminoethanethiol (AET), 4,4'-dithiodibutyric acid (DDA), and 11-mercaptoundecanoic acid (MUA) were deposited on the gold surface of QCM. In all monolayers, anti-CRP antibodies were immobilized such as Langmuir types because it had been introduced with a corresponding active group. According to the Langmuir isotherm equation amax, the maximum immobilized amounts of anti-CRP antibody were 4.27, 2.72, and 3.74 pmol/cm2, respectively. Although the immobilized amount of anti-CRP antibody was highest on the AET monolayer, the amount of antigen-antibody binding between the anti-CRP antibody and the CRP was highest on the MUA monolayer. CRP was detected from negative to positive levels when the calibration curve was achieved using MUA monolayer

Piezoelectric sensors for dioxins: a biomimetic approach

The aim of this work was to design a fast, cheap and easy to use analytical system for dioxins. Piezoelectric sensors coupled with the pentapeptides as biomimetic traps (the receptors), selective for the dioxins, were used for the realisation of this analytical system. A methodology to select specific receptors among all possible pentapeptides randomly generated was represented by the use of molecular modelling software. Three peptides called later on A, B and C (A:[N]Asn-Phe-Gln-Gly-Ile[C]; B:[N]Asn-Phe-Gln-Gly-Gln[C]; C:[N]Asn-Phe-Gln-Gly-Phe[C]), were selected and evaluated for their potential usage as artificial receptors in solid–gas analysis by using a quartz crystal microbalance (QCM) sensors array. The peptide sequences were functionalised by two terminal cysteine residues in order to achieve a covalent interaction with the QCM gold surface. A manganese–porphyrin complex and two other pentapeptides, a pentaglutamine (pentapeptide D) and a pentalysine (pentapeptide E), were used as negative control sensors. The QCM sensors (A, B and C) gave a good linearity against different sample concentrations of the 2,3,7,8-tetrachlorinated dibenzo- p-dioxin (TCDD) and a mixture of dioxins. In particular, the selectivity against 2,3,7,8-TCDD was nicely correlated to the estimated binding energy of the receptors calculcated by computational modelling. The cross-reactivity of the system was quantified using commercial polychlorinated biphenyls (PCBs) mixtures (dioxin-like compounds).

金表面の吸着水滴観察

The research of adsorption water on metal surfaces has been conducted mainly with FT-IR and QCM (Quartz Crystal Micro-balance). Among these methods, QCM has the high reliability as a research technique of adsorption water because of its relatively easy experiment. However, there has been no report on the direct observation of growth of water droplet or a water film on QCM surface. At present, therefore, it is difficult to understand the growth mechanism of water droplets or water film. In this study, the QCM measurement of adsorption water was carried out using a gold-coated quartz crystal. Moreover, for comparison with the QCM results, the non-contact mode AFM measurement was made by using an environmental cell that can control the relative humidity, and the nucleation and disappearance of water droplets were directly observed. As the results, the change in weight as a function of relative humidity by the QCM measurement was small when the gold surface of QCM was clean and few water droplets were present on the surface. It has been confirmed that the increase and decrease in weight depending on the relative humidity are due to the growth and shrink of adsorbed water droplets.