Functionalized Quartz Crystal Microbalance Sensor Research Articles

Chiral zinc oxide functionalized quartz crystal microbalance sensor for enantioselective recognition of amino acids

Chiral transition metal oxides with tunable structures and multiple physicochemical features have been increasingly applied for chiral sensing and detection. In this work, chiral zinc oxide (ZnO) was first applied as selector to construct quartz crystal microbalance (QCM) sensor for enantioselective recognition of amino acids. The chiral ZnO was prepared by a methionine-induced self-assembly strategy and its high topological chirality was confirmed by several techniques such as circular dichroism spectrum. The chiral discrimination factors were calculated by frequency shifts in response to aspartic acid, phenylalanine, lysine and arginine on L-ZnO surface, achieving 1.89 ± 0.04, 1.76 ± 0.11, 1.66 ± 0.07 and 1.54 ± 0.09, respectively. Notably, L-enantiomers preferred stronger absorptions on L-ZnO surface as compared to D-forms. It was further found that this sensor was appropriate for quantitative analysis and enantiomer excess analysis and adsorption kinetics study. Furthermore, molecular docking revealed the recognition mechanism, where chiral distinction was caused by the different steric interactions between enantiomers and chiral ZnO. This method enjoyed merits of high enantioselectivity, simple preparation and low cost, offering newly chiral sensing method for other molecules.

Graphene oxide/chitosan nanocomposite coated quartz crystal microbalance sensor for detection of amine vapors

Graphene oxide/chitosan (GO/CS) nanocomposite was synthesized using a facile method and employed as the sensing material of a quartz crystal microbalance (QCM) sensor to detect amine vapors. Scanning election microscopy (SEM), Fourier transform infrared spectrometer (FT-IR) and UV–visible spectra analysis were performed to characterize the morphology and physicochemical properties of the nanocomposite. The GO/CS obtained was in a porous mesh structure composed of interconnected nanofibers with diameters of approximately 50nm. A GO/CS functionalized QCM sensor was fabricated and its sensing properties were investigated. Being tested at room temperature, the sensor exhibited high sensitivity to aliphatic amines including methylamine (MA), dimethylamine (DMA) and trimethylamine (TMA), with the sensitivity values of 2.7, 2.3 and 4.8Hz/ppm, respectively. Their detection limits were all below 3ppm. The sensor maintained reasonable reversibility, repeatability as well as long-term stability. Combining the specific adsorption properties of chitosan (CS) with some inherent properties of graphene oxide (GO), the GO/CS coated sensor also performed favorable selectivity, especially for MA, DMA and TMA. The sensing mechanism might involve an adsorption–desorption process mainly caused by hydrogen bonding of the protonated amine and hydroxyl sites of the GO/CS film with the amine vapors. The underlying analyte sorption properties were further investigated based on the linear solvation energy relationship (LSER) model. This work might contribute to the future development of sensors for detection of amine vapors and broaden the application of GO and CS composite materials.

ADSORPTION KINETICS OF Cd2+ IONS ONTO MgPz THIN FILM

A (2,3,7,8,12,13,17,18-Octakis(4-tert-butylbenzylthio)-porphyrazinato)Mg(II) functionalized quartz crystal microbalance sensor has been developed for the detection of trace Cd 2+ ions in water samples. The quartz crystal microbalance results indicated that the MgPz coated sensor exhibited high sensitivity, stability and selectivity for the detection of Cd 2+ in aqueous solution. The lowest detection limit can reach 10 m g/ml Cd 2+ in aqueous solution, which resulted in the frequency shift of ~ 150 Hz. The observed adsorption data were analyzed using four adsorption kinetic models; the Elovich equation, Ritchie’s equation, pseudo first- and second-order equations. Results show that the linear regression analysis with respect to pseudo-second-order rate equation generates a straight line that best fit to the data of adsorption of Cd 2+ on Pz film.

Novel 4,4′-{(diphenylmethylene) bis(4,1-phenylene)bis(oxy)}-bridged ball-type phthalocyanines: Electrochemical, electrocatalytic oxygen reducing and heavy metals ions sensing properties

Novel 4,4′-{(diphenylmethylene)bis(4,1-phenylene)bis(oxy)} bridged ball-type metal-free, zinc(II), cobalt(II) and iron(II) ball-type metallophthalocyanines were achieved by the reaction of the bisphthalonitrile derivative in 2-dimetylaminoethanol. The isolation of the metal-free and metallophthalocyanines were carried out by both planar and column chromatography and also by hot soxhalet extraction. Their structures have been characterized by infrared, ultraviolet-visible,1H nuclear magnetic resonance and matrix assisted laser desorption/ionization mass spectroscopies. The redox characters of the ball-type metallophthalocyanines have been investigated by cyclic voltammetry, square wave voltammetry, controlled potential coulometry and spectroelectrochemistry in nonaqueous media. The investigation suggested that the ball-type complexes form ring-based and/or metal-based mixed-valence species as a result of the remarkable interaction between the two Pc rings and/or metal centers. Furthermore, these species were found to be stable as evidenced by the splitting of the relevant redox processes. The electrocatalytic oxygen reducing performances of the dinuclear ball-type complexes were also studied. The compound involving Fe(II) centers at the phthalocyanine cores displayed higher catalytic performance towards oxygen reduction than those of other ones. By using these compounds as sensing materials, a flow type quartz crystal microbalance sensor was developed for the detection of small concentrations of heavy metal ions. A cadmium ion sensitivity of 2.85 × 104Hz/mg.L[Formula: see text] was observed with ball-type iron(II) phthalocyanine coated quartz crystal microbalance sensor. Detection of other metal ions including Fe[Formula: see text], Zn[Formula: see text], Ag[Formula: see text] and Sn[Formula: see text] were also performed. The results indicated that 1– 4 functionalized quartz crystal microbalance sensors can be used for the detection of heavy metal ions in aqueous solution. Partition coefficients obtained from the linear response regimes of the calibration curves are in the 8.6 × 104–5.4 × 105range. Results show that the minor structural difference between metal free and metallophthalocyanine poses significant impact on metal ion partitioning.

Tailoring the structure of metal oxide nanostructures towards enhanced sensing properties for environmental applications

The present article reviews recent works in our laboratory about the sensing properties to toxic gases using nanostructured WO3, TiO2, FTiO2, and CuO functionalized quartz crystal microbalance (QCM) sensors. WO3 and TiO2 functionalized QCM sensors have much shorter response time than those functionalized by conventional hydrogen-bond acidic branched copolymers for detection of dimethyl methylphosphonate (DMMP). FTiO2 functionalized QCM sensors can improve the gas sensing characteristics by shortening the response time but at the price of partial irreversibility. The sensing mechanism was examined by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Varied CuO nanostructures were synthesized by simple modulation of reaction conditions. All the as-prepared CuO was applied on QCM resonators and explored for HCN sensing. Surprisingly, responses of all the sensors to HCN were found to be in an opposite direction as compared with other common volatile substances, offering excellent selectivity for HCN detection. The sensitivity was very high, and the response and recovery were very fast. Comparison of the specific surface areas of CuO nanostructures showed that CuO of higher surface area is more sensitive than that of lower surface area, indicating that the specific surface area of these CuO nanostructures plays an important role in the sensitivity of related sensors. Based on experimental results, a sensing mechanism was proposed in which a surface redox reaction occurs between CuO and Cu2O on the CuO nanostructures reversibly upon contact with HCN and air, respectively. The CuO functionalized QCM sensors are considered to be a promising candidate for trace HCN gas detection in practical applications.

Single crystal WO 3 nanoflakes as quartz crystal microbalance sensing layer for ultrafast detection of trace sarin simulant

Tungsten oxide (WO 3) nanoflakes were synthesized, and characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. Thermogravimetry and X-ray photoelectron spectroscopy demonstrate the existence of strongly bound surface water molecules on the surface of tungsten oxide nanoflakes. WO 3 nanoflake functionalized quartz crystal microbalance sensors were fabricated, and firstly used for detection of trace sarin simulant, dimethyl methylphosphonate (DMMP). The sensors have better reproducibility and stability as well as much shorter response (30 s) and recovery time (73 s) than those functionalized by conventional hydrogen-bond acidic branched copolymers. The strongly bound surface water molecules on the surface of WO 3 nanoflakes are believed to play a key role in achieving such excellent DMMP sensing characteristics.

Rapid detection of Bacillus anthracis using monoclonal antibody functionalized QCM sensor

Since the anthrax spore bioterrorism attacks in America in 2001, the early detection of Bacillus anthracis spores and vegetative cells has gained significant interest. At present, many polyclonal antibody-based quartz crystal microbalance (QCM) sensors have been developed to detect B. anthracis simulates. To achieve a simultaneous rapid detection of B. anthracis spores and vegetative cells, this paper presents a biosensor that utilizes an anti- B. anthracis monoclonal antibody designated to 8G3 (mAb 8G3, IgG) functionalized QCM sensor. Having compared four kinds of antibody immobilizations on Au surface, an optimized mAb 8G3 was immobilized onto the Au electrode with protein A on a mixed self-assembled monolayer (SAM) of 11-mercaptoundecanoic acid (11-MUA) and 6-mercaptohexan-1-ol (6-MHO) as adhesive layer. The detection of B. anthracis was investigated under three conditions: dip-and-dry, static addition and flow through procedure. The results indicated that the sensor yielded a distinct response to B. anthracis spores or vegetative cells but had no significant response to Bacillus thuringiensis species. The functionalized sensor recognized B. anthracis spores and vegetative cells specifically from its homophylic ones, and the limit of detection (LOD) reached 10 3 CFU or spores/ml of B. anthracis in less than 30 min. Cyclic voltammogram (CV) and scanning electronic microscopy (SEM) were performed to characterize the surface of the sensor in variable steps during the modification and after the detection. The mAb functionalized QCM biosensor will be helpful in the fabrication of a similar biosensor that may be available in anti-bioterrorism in the future.

Detection of Folate Binding Protein with Enhanced Sensitivity Using a Functionalized Quartz Crystal Microbalance Sensor

In this report, we describe the development of a quartz crystal microbalance biosensor for detection of folate binding protein (FBP). Using a simple folate-BSA conjugate adsorbed onto a Au-coated quartz sensor, a detection limit of 30 nM was achieved. Binding of FBP to the sensor surface could be blocked at concentrations as high as 1 microM with a 100-fold excess of folic acid, indicating the specificity of the folate-FBP interaction and the absence of nonspecific binding to the functionalized surface. Moreover, capture could be achieved in the presence of blood serum, making the assay amenable to the analysis of bodily fluids. Further signal enhancement based on an anti-FBP antibody and protein-A-coated gold nanosphere sandwich assay extended the detection limit to 50 pM (approximately 3 orders-of-magnitude improvement). Given the overexpression of FBP in certain malignancies and inflammatory disorders, we expect the methodology described here to be useful to detect FBP as a possible biomarker for disease diagnosis.