A quartz crystal microbalance sensor for the determination of nitroaromatics in landfill gas

A new sensor based on oxidative combustion of nitroaromatics to NO₂ and its detection with a quartz crystal microbalance (QCM) coated with copper phthalocyanine (CuPc) was developed for determination of nitroaromatics in landfill gas. An alternative method based on gas chromatography–mass spectrometry (GC–MS) was also used in order to assess the performance of the proposed method. The results show that the analytical apparatus based on the QCM is less expensive than the GC–MS, and that the analytical error is 0.8% for both methods.     

Immunodetection by quartz crystal microbalance

Biodetection is one of the most important challenges for the twenty-first century: many fields are concerned, mainly environmental and medical. The quartz crystal microbalance (QCM) may offer great possibilities for this purpose: a direct response signal, which characterizes the binding event between a sensitive layer, immobilized onto the surface transducer, and the analyte to be detected, can be obtained. However, for the detection of small biomolecules such as antigens, it is quite difficult to obtain an observable signal that corresponds directly to the binding event. In general, this is owing to the lack of mass sensitivity of the commonly used QCM, with 5- to 10-MHz quartz crystals. For improving this mass sensitivity, a 27-MHz quartz resonator was developed and incorporated in a flow-through microcell. Two biospecies, IgG rabbit and peroxidase enzyme, were studied with this ultra-sensitive QCM in terms of specificity, detection limit, and calibration curve.     

Reusable chromium-coated quartz crystal microbalance for immunosensing

The application of oxidized chromium as a reusable platform for the development of immunosensors is presented. Chromium films were deposited on quartz crystal microbalances to study the affinity interaction between rabbit immunoglobulin G (IgG) and goat anti-rabbit IgG. A covalent approach, based on the silane chemistry, was followed for the grafting of either the rabbit IgG or the anti-rabbit IgG on the silane-modified chromium surface. Next the differences between the deposition of rabbit IgG on immobilized anti-rabbit IgG and the deposition of anti-rabbit IgG on immobilized rabbit IgG were investigated. The chromium layer could be reused between experiments, after the proper removal of the organic layers with piranha etch, obtaining a high repeatability in the steps of the functionalization protocol.     

石英晶体微天平的新进展

石英晶体微天平（quartz crystal microbalance,QCM）是一种对界面变化敏感的仪器,它已经在物理、化学、生物学、药物学、临床医学、环境科学等学科的界面问题研究中得到了一定的应用.然而,QCM在液相下的应用和推广一直受限于QCM数据定量解释的困难.为此,科研工作者发展了多种高级的QCM,比如带阻抗分析功能的QCM（impedance QCM,i-QCM）或带能量耗散监测功能的QCM（QCM with dissipation,QCM-D）,同时还发展了许多相应的理论模型.但是,对于多数生物、化学工作者来说,这些理论过于复杂.这极大地限制了QCM的推广和潜力发挥.本文以我们小组在QCM方面的研究工作为线索,对已报道的分析方法、模型和方程按5类应用条件进行了整理,给出了明确的界定标准：它们是：1,固-气界面;2,牛顿流体;3,固-液界面的薄膜;4,固-液界面厚膜;5,固-液界面超厚膜.对于每一类情况,我们将用通俗易懂的语言描述如何对QCM数据进行简化却又保证研究精度需要的定量分析.对于液态环境下的QCM数据的分析,我们着重介绍了＂固化水层＂模型,该模型允许QCM在一定的条件下成为一把＂分子尺＂,工作范围从几个纳米到数百纳米.该分子尺在多个创新界面问题研究中得到很好的应用.最后,我们从理论上分析了QCM作为生物传感器的先天缺陷--因基于面均质量检测的原理,QCM技术对溶液中蛋白的检测下限仅在1μg mL-1数量级.进一步,我们探索了QCM的发展方向和潜在应用领域,希望籍此能进一步推广QCM在各个学科界面问题中的研究应用.     

Immunosensor for okadaic acid using quartz crystal microbalance

An immunosensor for the determination of okadaic acid (OA) using a quartz crystal microbalance (QCM) was developed and optimised in standard solutions. Several coupling techniques, protein A, protein G and polyethylenimine (PEI) with glutaraldehyde (GA) cross-linking, were investigated for the determination of okadaic acid and a very good result was obtained with PEI coupling. With the PEI coupling method, the optimisation of incubation time for the activation of PEI on the crystal surface using GA, the effect of the dilution factor of OA-bovine serum albumin (BSA) conjugate and the amount of antibody on crystal frequency were studied. Different molar ratios (4:1, 14:1, 30:1) of OA to bovine serum albumin for the conjugation were examined and the results using ELISA and a QCM showed that a ratio of 14:1 was slightly better than the other two. The strong attachment of the cross-linked complex to the gold surface resulted in an excellent storage lifetime of 38 days. However, the detection limit (1.9 μg/ml) and the sensitivity of the sensor were not satisfactory. Significant improvement of the performance of the device was obtained by incorporating an antibody-BSA hydrogel. Initial results showed that the minimum amount of analyte detectable and the sensitivity of the device were improved by 524- and 80-fold, respectively.     

A study of glycoprotein-lectin interactions using quartz crystal microbalance

A study of biospecific interactions between lectins and glycoproteins using a quartz crystal microbalance biosensor with dissipation monitoring (QCM-D) was reported. Four lectins were covalently immobilised on the thiol-modified gold electrode of the QCM chips in order to obtain sensing surfaces. The frequency shift served as analytical signal and the dissipation shift provided additional information about the viscoelastic properties of the glycoprotein-lectin complex formed on the surface of the QCM chip. The working conditions of the assay were optimised. The interaction between different lectins and glycoproteins was characterised by specific frequency shifts and each glycoprotein displayed its own unique lectin-binding pattern. This lectin pattern can serve as a finger print for the discrimination between various glycoproteins. The biosensor enabled quantitative determination of glycoproteins in the concentration range of 50 μg mL⁻¹ to 1 mg mL⁻¹ with good linearity and R.S.D. of less than 6.0%. An additional advantage of the proposed biosensor was the possibility to re-use the same lectin surfaces during a long period of time (2 month) without changes in analytical response. This was experimentally achieved by the application of a proper regeneration solution (10 mM glycine-HCl, pH 2.5). The lectin-based quartz crystal microbalance technique is suitable both for rapid screening and for quantitative assay of serum glycoproteins.     

A quartz crystal microbalance sensor for the detection of formic acid vapors

A new quartz crystal microbalance sensor is developed to determine formic acid at low concentrations. Four previously selected polymers with acid–base characteristics were tested as possible coatings. Polyoxyethylene bis [amine] presented the best results. The sensor is rapid, sensitive [0.67 Hz/(mg/m³)], and reversible at low concentrations. The detection limit for formic acid (7.2 mg/m³) is comparable with the short term exposure limit and the threshold limit values. It presents a fast mechanical response to pressure changes, so that it can be quickly used in different environments and situations. The sensor also shows a good stability in a temperature range typical of work atmospheres (16–36 °C). It has a wide linear range (7.2–911.2 mg/m³) and a long useful time. It is also applicable to other low molecular mass carboxylic acids such as acetic acid. Received: 26 September 2000 / Revised: 8 February 2001 / Accepted: 12 February 2001     

A quartz crystal microbalance sensor for the detection of formic acid vapors

A new quartz crystal microbalance sensor is developed to determine formic acid at low concentrations. Four previously selected polymers with acid-base characteristics were tested as possible coatings. Polyoxyethylene bis [amine] presented the best results. The sensor is rapid, sensitive [0.67 Hz/(mg/m3)], and reversible at low concentrations. The detection limit for formic acid (7.2 mg/m3) is comparable with the short term exposure limit and the threshold limit values. It presents a fast mechanical response to pressure changes, so that it can be quickly used in different environments and situations. The sensor also shows a good stability in a temperature range typical of work atmospheres (16-36 degrees C). It has a wide linear range (7.2-911.2 mg/m3) and a long useful time. It is also applicable to other low molecular mass carboxylic acids such as acetic acid.     

A new electrochemical cell adapted to quartz crystal microbalance measurements

As the resonance frequency of an oscillating quartz changes upon the deposition of a given mass to the crystal surface, it can be used as a very sensitive mass measuring device. Despite a growing interest in the use of electrochemical quartz crystal microbalance (EQCM), there is still no commercial available measurement cell which can satisfy all the conditions needed in electrochemical investigations. The design and characteristics of a new electrochemical cell adapted to EQCM measurements are presented. The sensitivity of the microbalance, which is determined by several calibration runs of silver electrodeposition is (183.2±2.9) Hz μg⁻¹ cm². This value, which is close to the theoretical one, confirms the validity of the system we have developed. The calibration procedure and the EQCM using range are then discussed.     

A quartz crystal microbalance study on a metallic nickel electrode

Electrochemical processes taking place on a Ni electrode have been investigated with the electrochemical quartz crystal microbalance. At potentials negative of ca. –500 mV vs. SCE, a closed frequency loop is observed without irreversible changes in the mass of the electrode. The phase transition - -Ni(OH)₂, taking place at potentials positive to –500 mV vs. SCE, is accompanied by an irreversible increase in the mass of the electrode. When Ni(OH)₂ is further oxidized, the frequency increase is followed by a decrease, indicating the transport of various species in both directions, i.e. from and into the electrode. During the Ni(OH)₂ oxidation reaction the transport of species responsible for the mass increase is slower than the charge transfer process.Contribution to the 3rd Baltic Conference on Electrochemistry, GDASK-SOBIESZEWO, 23–26 April 2003. Dedicated to the memory of Harry B. Mark, Jr. (February 28, 1934–March 3rd, 2003)     

Lectin-carbohydrate affinity measured using a quartz crystal microbalance

The association of two molecules is described by two parameters, association equilibrium and association rate constants, which are characteristic for a given type of interaction. Usually, they are determined for interacting molecules dissolved in solution. However, for many applications one type of molecules is immobilized on a substrate, which may influence the binding kinetics. The studied complex of concanavalin A and carboxypeptidase Y belongs to the lectin-carbohydrate type of interaction involving the recognition of oligosaccharide moieties. The concanavalin A was immobilized on a gold electrode of quartz crystal, while carboxypeptidase Y was added to a buffer (Tris-buffered saline). The constants describing the association of the investigated molecules were determined on the basis of measurements performed using a quartz crystal microbalance in liquid. The obtained values were (0.59+/-0.01)x10(6) M(-1) for the association equilibrium constant and (5.6+/-0.1)x10(4) M(-1)s(-1) for the association rate constant. The saturation binding experiment gave another value of the association constant, (2.7+/-0.02)x10(6) M(-1). The comparison of obtained values with previously published ones verifies that the molecule orientation and binding site accessibility for specific ligands could influence the association equilibrium constant value. The presented measurements demonstrate the ability of a quartz crystal microbalance to detect and to evaluate the association process occurring between molecules.     

Adsorbed liposome deformation studied with quartz crystal microbalance

Deformation of surface-adsorbed liposomes is an important parameter that governs the kinetics of their transformations, but one that is very difficult to measure in the case of nm-size liposomes. We investigate the deformation of dimyristoyl phosphatidyl choline liposomes by quartz crystal microbalance (QCM) as a function of temperature and show that it follows the dependence of this lipid's bending modulus on temperature, as expected from theoretical considerations. To corroborate our approach, we model QCM response from adsorbed liposomes by explicitly considering their shape and mechanical properties.     

A review of monolithic multichannel quartz crystal microbalance: a review

Monolithic multichannel quartz crystal microbalance (MQCM) is an emerging technology for advanced sensing and measurement applications. In this report, a comprehensive review of MQCM technology is presented. Firstly, basic MQCM's design, simulation and characterization with emphasis on acoustic interference are described. Next, various MQCM schemes to minimize interference and enhance sensitivity of conventional MQCM devices based on modification of quartz substrate structure are digested. These include mesa, convex and x-axis inversion structures. Three important MQCM sensing platforms and their application areas are then discussed. These comprise MQCM as a static multichannel detector, series MQCM as a multichannel detector for the flow injection analysis and multi-frequency QCM for multi-sensitivity/multi-dynamic range detection. Finally, potential MQCM applications including electronic noses, bio-sensor arrays, and photocatatalytic measurement are illustrated and prospective MQCM applications including electronic tongues and electrochemical measurement are suggested.     

Gas-phase pre-concentration for a quartz crystal microbalance based electronic nose

The effect of different relative humidity (RH) on the response of a six-polymer coated Quartz Crystal Microbalance (QCM) sensor based electronic nose (EN) was investigated, RH 30 and 50% respectively. Increases in the sensor responses were observed for an increase in RH. A stainless steel pre-concentration tube (PCT) containing Porapak-S and a nichrome heating element was developed to minimise the effect and allow for chromatographic pre-separation. Breakthrough times of chemical compounds through the PCT were experimentally determined and used to select a mixture of water and toluene as a suitable sample for pre-separation. The PCT was capable of separating the water from the toluene and the EN was competent at evaluating the concentration of toluene in the solution.This revised version was published online in November 2005 with corrections to the Cover Date.     

Development of a sensor for calcium based on quartz crystal microbalance

A new sensor for calcium based on a piezoelectric quartz crystal is presented. The selectivity depends on the ratio lipophilic salt/ionophore of the composition of the coating of the quartz crystal. A crystal coated with a THF solution of PVC (34.5% w/w), DOS (62.1% w/w) and 10,19-bis[(octadecylcarbamoyl) methoxyacetyl]-1,4,7,13,16-pentaoxa-10,19-diaza cycloheneicosane (3.4% w/w) and a salt/ionophore molar proportion of 60%, corresponding to a frequency decrease of the dry crystal of 6.0 kHz, showed a detection limit to calcium of 2.2 mg/L. Both a standard calcium chloride solution and a commercially balanced salt solution for tissue culture were analyzed subsequent to ion chromatographic separation. The results obtained with the sensor developed were compared with those obtained with a conductivity detector. Although the results from both detectors agreed for the standard solution, only the quartz crystal sensor was able to give reliable results for the tissue culture solution.     

Biofouling of dextran-derivative layers investigated by quartz crystal microbalance

This study reports the fouling of carboxymethyl dextran (CMD) layers in cell culture medium, fibronectin, and serum solutions. CMD layers were covalently immobilized onto amine groups available either on an n-heptylamine plasma polymer (HApp) layer or onto a polyethylenimine (PEI) coating grafted to an acetaldehyde plasma polymer (AApp) layer. The successful immobilization of the graft layers was demonstrated by X-ray photoelectron spectroscopy (XPS). Primary amines on HApp and AApp + PEI surfaces were quantified using a colorimetric assay. Quartz crystal microbalance (QCM) was used to investigate in real-time the fouling of the graft layers upon incubation in cell culture medium (RPMI), fibronectin, and foetal bovine serum (FBS) solutions. HApp, AApp and AApp + PEI layers exhibited large fouling in fibronectin and FBS solutions, while fouling in RPMI cell culture medium was not significant. Protein repellent properties of CMD layers in FBS and fibronectin have been demonstrated compared to the other tested surfaces. QCM has shown that both CMD layers were fouled to a small extent in RPMI medium.     

The quantification of potassium using a quartz crystal microbalance

N,N'-dibenzyl-4,13-diaza-18-crown-6 (A) and bis[(benzo-15-crown-5)-4'-ylmethyl] pimelate (B) were tested as coatings for two piezoelectric crystals for potassium quantification. Both sensors showed stability, reversibility and sensitivity characteristics that allowed their use in quantitative analysis. However, compound A is much more sensitive to potassium than B. Compound A also shows a larger relative sensitivity for potassium with regard to sodium than B. A pharmaceutical sample of known composition was analysed both by an acoustic wave sensor with a crystal coated with compound A and by conductivity. No statistically significant difference in the median of the results was found (alpha = 0.05), although precision is superior for the conductivity methodology. Performance of the sensor in terms of frequency stability and selectivity was improved by the incorporation of PVC, a plasticizer and a lipophilic salt in the coating composition. Limits of detection found for potassium were 1.92 ppm, or 1.75 ppm for a crystal with a frequency decrease due to coating of 2.9 kHz or 3.9 kHz, respectively. Selectivity coefficients (fixed interference 80 ppm) for potassium over Na, Ca, Al, Zn, Mg, and Fe ranged from 0.103 to 0.332.     

Development of a sensor for calcium based on quartz crystal microbalance

A new sensor for calcium based on a piezoelectric quartz crystal is presented. The selectivity depends on the ratio lipophilic salt/ionophore of the composition of the coating of the quartz crystal. A crystal coated with a THF solution of PVC (34.5% w/w), DOS (62.1% w/w) and 10,19-bis[(octadecylcarbamoyl) methoxyacetyl]-1,4,7,13,16-pentaoxa-10,19-diaza cycloheneicosane (3.4% w/w) and a salt/ionophore molar proportion of 60%, corresponding to a frequency decrease of the dry crystal of 6.0 kHz, showed a detection limit to calcium of 2.2 mg/L. Both a standard calcium chloride solution and a commercially balanced salt solution for tissue culture were analyzed subsequent to ion chromatographic separation. The results obtained with the sensor developed were compared with those obtained with a conductivity detector. Although the results from both detectors agreed for the standard solution, only the quartz crystal sensor was able to give reliable results for the tissue culture solution.     

Electrochemical quartz crystal microbalance studies of redox polymer films

Electrochemical quartz crystal microbalance measurements are reported for redox switching of thin films of three macromolecule-metal complexes: poly(vinylferrocene) (PVF), 10% osmium-functionalized poly(vinylpyridine) (Os-PVP), and 10% osmium functionalized poly(vinylpyridine-co-styrene) (Os-PVP-co-PS). The data provide insight into the ion and solvent transfer processes associated with electron transfer between the electrode and the electroactive film. Four important parameters are identified: electrolyte composition, (co)polymer composition, prior film history and experimental time scale.     

Optimization of dispersive liquid-liquid microextraction combined with gas chromatography for the analysis of nitroaromatic compounds in water

Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-flame ionization detector (GC-FID) was developed for preconcentration and determination of some nitroaromatic compounds in wastewater samples. The effects of different variables on the extraction efficiency were studied simultaneously using experimental design. The variables of interest in the DLLME process were extraction and disperser solvent volumes, salt effect, sample volume, extraction temperature and extraction time. A Plackett-Burman design was performed for screening of variables in order to determine the significant variables affecting the extraction efficiency. Then, the significant factors were optimized by using a central composite design (CCD) and the response surface equations were derived. The optimum experimental conditions found from this statistical evaluation included: sample volume, 9 mL; extraction solvent (CCl₄) volume, 20 μL; disperser solvent (methanol) volume, 0.75 mL; sodium chloride concentration, 3% (w/v); extraction temperature, 20 °C and extraction time, 2 min. Under the optimum conditions, the preconcentration factors were between 202 and 314. Limit of detections (LODs) ranged from 0.09 μg L⁻¹ (for 2-nitrotoluene) to 0.5 μg L⁻¹ (for 2,4-dinitrotoluene). Linear dynamic ranges (LDRs) of 0.5-300 and 1-400 μg L⁻¹ were obtained for mononitrotoluenes (MNTs) and dinitrotoluenes (DNTs), respectively. Performance of the present method was evaluated for extraction and determination of nitroaromatic compounds in wastewater samples in the range of microgram per liter and satisfactory results were obtained (RSDs < 10.1%).