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Investigation of Electrosorption of Organic Molecules onto Gold and Nickel Electrodes Using an Electrochemical Quartz Crystal Microbalance.

The adsorption behaviors of two organic molecules, benzoic acid (BA) and 2-butyne-1,4-diol (BD), on metal electrodes have been studied using an electrochemical quartz crystal microbalance (EQCM) combined with the cyclic voltammetry technique. In the range of potentials studied, BA molecules were adsorbed onto an electrodeposited gold electrode with a saturation concentration of 5.0 x 10(14) molecules/cm(2). It was found that the Frumkin isotherm model was most suitable to depict the electrosorption behavior. The isotherm parameters by nonlinear fitting, which agreed with the literature values, implied BA was chemisorbed on the gold surface. For BD on an electrodeposited nickel electrode, the equivalent molar mass of the reaction species was calculated on the basis of the voltammetry curve and mass curve, which were obtained simultaneously during the potential scan. The analysis of EQCM data for the electrosorption of BD on gold and nickel electrodes showed an irreversible characteristic; the latter effectively inhibited the hydrogen evolution reaction. Copyright 1999 Academic Press.

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Surface Tension and Dynamic Contact Angle of Water in Thin Quartz Capillaries.

The surface tension of water has been measured in quartz capillaries with radii from 200 down to 40 nm. It appears that the surface tension does not differ from the known (bulk) values in the temperature range from 8 to 70 degrees C, within 1% experimental error. The dynamic contact angle, theta(d), vanishes when the capillary surface is covered with a wetting film left behind the receding meniscus. In the case of a dry surface, theta(d) depends on the velocity of the meniscus motion. The results obtained do not agree with presently available theoretical predictions from hydrodynamic theories of dynamic contact angles. Rather the kinetics of water vapor adsorption ahead of the moving meniscus seems to be the major controlling agent of the dynamic contact angle. Copyright 2000 Academic Press.

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Monitoring Protein Fouling of Metal Surfaces via a Quartz Crystal Microbalance.

A quartz crystal microbalance (QCM) has been used to study the fouling of chromium and hydrophobically modified gold surfaces when heated with milk proteins. Solutions of pure beta-lactoglobulin and a commercial skimmed milk powder were studied at 3 wt%, neutral pH, and before and after heating the solutions to 80 degrees C. The ease of removal of the adsorbed protein by rinsing with buffer and 1 wt% Tween 20 was also studied. The beta-lactoglobulin behaved rather similarly on the hydrophobic gold and chromium surfaces: Tween 20 was not particularly effective in removing this protein after heating. On the other hand, Tween 20 seemed more efficient at removing the heated skimmed milk protein from the hydrophobic gold surface, but less efficient at removing the skimmed milk from the chromium surface (which also exhibited the highest adsorbed amounts of either protein). On chromium, trypsin followed by buffer removed almost all the beta-lactoglobulin but had little effect on the adsorbed layers from skimmed milk. These changes are interpreted in terms of the hydrodynamic thickness of the adsorbed films and lead to the conclusion that the QCM is a highly sensitive way of monitoring adsorbed film properties during heating, cooling, and detergent action. Copyright 2000 Academic Press.

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Study of the Adsorption of Glutathione on a Gold Electrode by Using Electrochemical Quartz Crystal Impedance, Electrochemical Impedance Spectroscopy, and Cyclic Voltammetry.

Adsorption of a biological peptide, glutathione, on a gold electrode was studied by using electrochemical quartz crystal impedance (EQCI), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) techniques. The time courses of responses of piezoelectric and electrochemical impedance parameters were simultaneously obtained during the adsorption processes of the two forms of peptide, oxidized and reduced glutathione. It was found that the frequency curve due to the oxidized glutathione (GSSG) adsorption exhibited a character of a sum of two exponential functions. For reduced glutathione (GSH), the frequency adsorption curve could be expressed by a first-order reaction kinetic model and the corresponding kinetic parameters at different amounts of GSH were obtained. The heterogeneous charge-transfer rate constants of ferricyanide/ferrocyanide before and after the peptide adsorption were determined by CV and EIS methods, respectively. According to the simple equivalent electric network of the electrochemical interface, the electrochemical impedance parameters were also obtained. The results showed that the proposed method should be found in wider applications in interfacial biochemistry studies since these combined techniques have advantages in real time multidimensional information including electrochemical and electrochemical impedance parameters. Copyright 2000 Academic Press.

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Transport of Iron Oxide Colloids in Packed Quartz Sand Media: Monolayer and Multilayer Deposition.

The transport and deposition dynamics of hematite (alpha-Fe(2)O(3)) colloids in packed quartz sand media are investigated. Column transport experiments were carried out at various solution ionic strengths, colloid concentrations, and flow velocities. A colloid transport model was proposed that includes the dynamics of blocking as well as multilayer deposition that takes place at high ionic strengths where particle-particle interactions are favorable. Blocking dynamics in the model are described by either Langmuirian adsorption (LA) or random sequential adsorption (RSA). Two important model parameters-the particle-matrix collision efficiency and the ionic strength dependent blocking (excluded area) parameter-are estimated from the colloid breakthrough curves using a nonlinear optimization procedure. The collision (attachment) efficiency for particle-particle interactions, on the other hand, was determined independently from colloid aggregation rate measurements. At very low ionic strength, only monolayer deposition is observed and the RSA model gives a better description of the experimental data than the LA model. At higher ionic strengths, multilayer deposition becomes significant and both models yield comparable results. Calculated maximum surface coverages at low ionic strengths were in good agreement with experimentally observed values obtained by scanning electron microscopy. Copyright 2000 Academic Press.

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Comparative Behavior of Aromatic Disulfide and Diselenide Monolayers on Polycrystalline Gold Films Using Cyclic Voltammetry, STM, and Quartz Crystal Microbalance.

A comparative investigation of the self-assembled monolayers of diphenyl disulfide (DDS), diphenyl diselenide (DDSe), and naphthalene disulfide (NDS) on polycrystalline gold films using STM, QCM, and electrochemical techniques is presented. The geometric constraint imposed by the rigid naphthalene ring for NDS inhibits the cleavage of the S-S bond, thus adversely affecting the monolayer organization and stability relative to the monolayers formed with DDS and DDSe. A comparative analysis using techniques like cyclic voltammetry and quartz-crystal microbalance indicates that, for DDS, the facile cleavage of the S-S bond leads to strong binding of the adsorbate molecules at the preferred surface sites, resulting in a rather well-organized self-assembled structure. The STM pattern of NDS reveals a periodic domain (i.e., less than 10 nm in size) while no such small domains are seen in the case of DDS and DDSe due to the orientational flexibility of the rings. Copyright 2001 Academic Press.

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In Situ Monitoring of Generation and Precipitation of Ferric Hydroxide Sol with a Piezoelectric Quartz Crystal Impedance Analyzer.

The piezoelectric quartz crystal (PQC) impedance technique was applied to monitor in situ generation and precipitation of the ferric hydroxide sol in aqueous solutions at 90 degrees C. Equivalent circuit parameters and resonant frequencies as well as the half-peak width of the electroacoustic conductance spectrum deltaf(G1/2) for the PQC resonance were obtained and analyzed. Three stages, sol generation and simultaneous adsorption, adsorption equilibrium, and precipitation of ferric hydroxide sol could be identified in the process of adding the ferric nitrate solution into the hot water. A scheme of two consecutive reactions occurring at the electrode/solution interface was used to analyze the adsorption kinetics of ferric hydroxide sol onto the Au electrode. In addition, the electrolyte-induced precipitation of the colloid was monitored and discussed. Temperature effect on the PQC resonance behavior in liquid was also investigated. Since the PQC impedance technique provides multidimensional piezoelectric information in situ, it is highly recommended for studying the process of sol-gel generation and precipitation. Copyright 2001 Academic Press.

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Adsorption of a diverse set of organic vapors on quartz, CaCO3, and alpha-Al2O3 at different relative humidities.

Adsorption constants of a diverse set of 50 organic vapors have been measured on quartz (SiO(2)), CaCO(3), and alpha-Al(2)O(3) at different relative humidities at 15 degrees C. For nonpolar compounds we found an exponential decrease of the adsorption constants on a given mineral between 40 and 97% relative humidity. Extrapolated to 100% relative humidity, the adsorption constants of nonpolar compounds on the different minerals coincide and agree with those measured on a bulk water surface. The adsorption constants of polar compounds also decrease with increasing humidity up to 90%, but between 90% and 100% they increase again. We speculate that this effect is due to a change in the orientation of the water molecules that form the surface at which the organic vapors adsorb at this high humidity. The compound variability in the adsorption constants of all compounds on a given surface at a given relative humidity could be described rather well with a linear free energy relationship using Abraham's solvation parameters for the van der Waals and electron-donor/acceptor properties of the compounds. The remaining deviation between fitted and experimental data was found to be systematic, which indicated that an optimized parameter set for the used compounds could still considerably improve the fit.

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A comparative study of surfactant adsorption on model surfaces using the quartz crystal microbalance and the ellipsometer.

The nature of hexaethylene glycol mono-n-tetradecyl ether (C(14)EO(6)) layers adsorbed onto different model surfaces was systematically investigated by means of QCM-D (quartz crystal microbalance-dissipation) and ellipsometry. The amount of non-ionic surfactant adsorbed is determined both at hydrophilic and hydrophobic surfaces. In particular, the substrates employed were hydrophilic silica, hydrophobized silica (using dimethyldichlorosilane), and hydrophobized gold surfaces (using 10-thiodecane and 16-thiohexadecane). It was shown that the frequency shift obtained from the QCM-D experiments results in an overestimation of the adsorbed mass. This is attributed to two different effects, viz. water that is coupled to the adsorbed layer due to hydration of the polar region of the surfactant and second water that for other reasons is trapped within the adsorbed layer. Furthermore, from the ellipsometry data the adsorbed layer thickness is determined. By combining the thickness information and the dissipation parameter (obtained from the QCM-D experiments), we note that the dissipation parameter is insufficient in describing the viscoelastic character of thin surfactant films.

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Transport of kaolinite colloids through quartz sand: influence of humic acid, Ca(2+), and trace metals.

To evaluate the risk of contaminant transport by mobile colloids, it seems essential to understand how colloids and associated pollutants behave during their migration through uncontaminated soil or groundwater. In this study, we investigated at pH 4 the influence of flow velocity, humic acid, solution Ca(2+) concentrations, and trace metals (Pb(2+), Cu(2+)) on the transport and deposition of kaolinite particles through a pure crystalline quartz sand as porous medium. A short-pulse chromatographic technique was used to measure colloid deposition. Adsorption of humic acid to the kaolinite increase its negative surface charge and then decrease colloid deposition. Experiments with different flow rates showed that humic-coated kaolinite colloid deposition followed a first-order kinetic rate law. The deposition rate coefficients of humic-coated kaolinite colloids increase with increasing Ca(2+) concentration in the suspension. The effect of trace metals on the mobility is studied by injecting two suspensions with different concentrations of Pb(2+) and Cu(2+). At very low cation concentration, the fraction of colloids retained is low and roughly independent of the nature of divalent cations. At high concentration, the deposition is higher and depends on the affinity of divalent cations toward humic-coated kaolinite colloids.

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Determination of trace elements in quartz glass by use of LINA-Spark-ICP-MS as a new method for bulk analysis of solid samples.

The determination of trace elements in pure quartz glass samples has been performed by coupling an ICP quadrupole mass spectrometer with the LINA-Spark-Atomizer, an IR laser ablation system dedicated to direct bulk and surface analysis of solid samples. Linear calibration curves were obtained for nine elements (Na, Al, Ca, Ti, Cr, Mn, Zr, Ba, and Pb) in the ng g(-1) range with detection limits of less than 10 ng g(-1) for Ca, Cr, Mn, Zr, Ba, and Pb and in the range of 120-220 ng g(-1) for Na, Al, and Ti. The distance between the laser focal point and the sample surface has a significant influence on signal intensity and precision, both of which can be improved by a factor of approximately two by focusing the laser 15 mm behind the sample surface. Aerosol moistening reduced the standard deviation of the signal intensity by a factor of 2-4. Signal instability, which resulted from different ablation rates or variations in the transmission of the mass spectrometer, were compensated by use of the simultaneously measured SiAr+ ion as an internal standard. Under these conditions precision was usually better than 5% RSD. The results were compared with those obtained by use of a commercial LA-ICP-MS system. With this instrumentation linear calibration curves were achieved for three elements only (Al, Ti, and Pb), showing that LA-ICP-MS is less appropriate for bulk analysis in the ng g(-1) range.

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Chiral discrimination of limonene by use of beta-cyclodextrin-coated quartz-crystal-microbalances (QCMs) and data evaluation by artificial neuronal networks.

The enantiomeric composition of the chiral flavoring agent limonene was analyzed by means of a quartz-crystal microbalance (QCM) sensor. As chiral selectors three different modified beta-cyclodextrins were investigated. The selector molecules were applied as mixtures in different polysiloxane matrices. The chiral separation factors alpha for limonene obtained at 30 degrees C by gas chromatography and by use of the QCM sensor were comparable. Evaluation of sensor data was performed by use of an artificial neuronal network (ANN); this enabled prediction of the enantiomeric composition of the gas mixtures.

Cyclodextrins↗

Comparison of cold-quartz ultraviolet, low-energy laser, and occlusion in wound healing in a swine model.

A randomized, blind, controlled study used six pigs to examine the effectiveness of low-energy HeNe laser irradiation (632.8nm), cold-quartz UV (254nm), occlusion, and exposure in the treatment of full thickness skin wounds. Laser-treated wounds received a nominal dose of 54mW daily on a schedule of six days/week, UV-treated wounds were given two minimal erythemal dose treatments, twice daily, six days a week, and occluded wounds were checked and dressings replaced as needed twice daily, six days a week. All wounds were treated until clinically healed. Time to closure, wound strength, and bacterial colonization were monitored. There were no complications. Although the laser-treated wounds healed faster than the exposed-control wounds (20.3 +/- 0.9 days vs 21.1 +/- 2 days), only the occluded wounds healed significantly (p less than or equal to 0.05) faster than the controls (18 +/- 1.6 days vs 20.6 +/- 1.4 days). No statistically significant difference in bacterial colonization or wound strength was noted although the occlusion-treated wounds tended to be the strongest.

Animals↗

Knoop hardness of ten resin composites irradiated with high-power LED and quartz-tungsten-halogen lights.

This study compared a high-power light-emitting-diode (LED) curing light (FreeLight 2, 3M ESPE) with a quartz-tungsten-halogen (QTH) light (TriLight, 3M ESPE) to determine which was the better at photo-polymerising 10 resin composites. Class I preparations were prepared 4-mm deep into human teeth and filled with 10 different composites. The composites were irradiated for 50% or 100% of their recommended times using the LED light, and for 100% of their recommended times with the QTH light on either the high or medium power setting. Fifteen minutes later, the Knoop hardness of the composites was measured to a depth of 3.5 mm from the surface. When irradiated by the LED light for their recommended curing times, the Knoop hardness of all 10 composites stayed above 80% of the maximum hardness of the composite to a depth of at least 1.5 mm; three composites maintained a Knoop hardness that was more than 80% of their maximum hardness to a depth of 3.5 mm. Repeated measurements analysis of variance indicated that all the two-way and three-way interactions between the curing light, depth, and composite were significant (p < 0.01). To eliminate the choice of composite as a factor, an overall comparison of the lights was performed using the Kruskal-Wallis test and distribution free multiple comparisons of the ranked hardness values. The LED light, used for the composite manufacturer's recommended time, was ranked the best at curing the composites to a depth of 3mm (p < 0.01). The LED light used for 50% of the recommended time was not significantly different from the QTH light used for 100% of the recommended time on the high power setting.

Composite Resins↗

Comparison between the surface plasmon resonance (SPR) and the quartz crystal microbalance (QCM) method in a structural analysis of human endothelin-1.

In this study, an automated surface plasmon resonance (SPR)-based biosensor was compared with a quartz crystal microbalance (QCM) biosensor. The two biosensor systems were used for characterizing a site-directed monoclonal antibody (mAb), raised against the C-terminal heptapeptide ET-1(15-21) of the human endothelin (ET-1). The mAb was characterized by its capacity for binding to ET-1, ET-3, Big.ET-1(22-38), the C-terminal (ET-1(15-21), ET-1(16-21), ET-1(17-21)), and six derivates of ET-1(16-21), each containing a substitution with alanine (Ala) of a single aminoacid from position 16-21, respectively. The mAb reacted well with ET-1 and its fragments ET-1(15-21), ET-1(16-21), ET-1(17-21), but showed only a partial cross-reaction with ET-3, and did not bind human Big.ET-1(22-38). The Ala substitution on position 16,17, or 19 of ET-1(16-21) did not affect the antibody binding capacity of the hexapaptide ET-1(16-21). On the contrary, Ala substitution or Asp(18), Ile(20) and particularly Trp(21), inhibited its immunoreactivity. Thus the C-terminal represents an immunodominant epitope in ET-1 and is important for antibody binding. The SPR and QCM response signals were similar in shape but differing in time scales, reflecting differences in detection mechanisms. With regard to the fundamental problem of comparing different measurement principles, we found a good correlation between results obtained using the BIA technology and the QCM.

Antigen-Antibody Complex↗

Synthesis of tethered-polymer brush by atom transfer radical polymerization from a plasma-polymerized-film-coated quartz crystal microbalance and its application for immunosensors.

This study synthesizes a tethered surface-grafted poly(acrylic acid) with quartz crystal microbalance (QCM) surfaces and provides detailed analysis of their properties and application. A tethered polyelectrolyte brush of poly(acrylic acid) is generated by first covering the substrate with a plasma-polymerized allyl alcohol (pp-AA) film, changing the polymerization initiators (bromination), and then grafting through atom transfer radical polymerization (ATRP) of tert-butyl acrylate (t-BA); these initiators are immobilized on a surface and exposed to a monomer. Finally, we convert the poly(t-BA) brush into poly(acrylic acid) through hydrolysis. We use the QCM technique to measure configuration change of the tethered poly(acrylic acid) grafted chains with two different degrees of polymerization (DP=50,200) in aqueous solutions at three different pH values (4.0, 4.8, and 5.4). The tethered poly(acrylic acid) grafted QCM shows that repeatable frequency responses are induced by pH change of solution. These frequency responses of large DP for pH are 20 times larger than responses of lower DP for pH. The frequency response of antibody immobilization on tethered poly(acrylic acid) grafted QCM (DP=200) and its frequency response of immunoreaction are 10 times larger than conventional immobilization methods by cysteamine with glutalaldehyde coupling of the antibody. The tethered poly(acrylic acid) grafted QCM can increase the frequency response for pH, the immobilization amount of antibody, and immunosensor response.

Acrylic Resins↗

Quartz crystal microbalance bioaffinity sensor for biotin based on mixed self-assembled monolayers and metastable molecular complex receptor.

A quartz crystal microbalance (QCM) sensor was proposed for the detection of small molecule biotin based on the mixed self-assembled monolayer (SAM) of thiols on gold substrate and the bioaffinity difference between an analyte (biotin) and an analogue compound (HABA) in binding avidin. Avidin formed a metastable complex with 2-[(4-hydroxyphenyl)azo]benzoic acid (HABA) immobilized on the crystal surface. When the sensor contacts a sample solution containing biotin, the avidin was released from the sensor surface to form a more stable complex with biotin in solution. The frequency change recorded is proportional to the desorbed mass of avidin, and there is a clear mathematic relationship between the frequency change and the biotin concentration. The use of mixed SAMs allows the stable attachment of bioreceptor molecules on the QCM, and enhances the amount of the immobilized molecules on the QCM, as a longer "space arm" in the mixed SAMs makes this monolayer membrane more accessible to capture the immobilized molecules. The proposed bioaffinity sensor has nice response to biotin in the range of 0.017-1.67 microg/mL. The sensor could be regenerated under very mild conditions simply by reimmersion of the sensor into a biotin solution to desorb the surplus avidin.

Azo Compounds↗

Quartz crystal microbalance bioaffinity sensor for rapid identification of glycosyldisulfide lectin inhibitors from a dynamic combinatorial library.

Carbohydrate-lectin interactions were probed with dynamic combinatorial libraries, using the plant lectin Concanavalin A as target species. The dynamic combinatorial libraries were generated from a pool of thiol components through reversible thiol-disulfide interchange, and screened using a simple and efficient method based on a quartz crystal microbalance setup. It was found that dimers based on 1-thio- and 6-thio-mannose analogues were the most active inhibitors. Furthermore, the results clearly show that the 6-thio-mannose possess unique characteristics compared to its oxygen-containing counterpart.

Biosensing Techniques↗