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Production of inositol phosphates and reactive oxygen metabolites in quartz-dust-stimulated human polymorphonuclear leukocytes.

The present paper explores phosphoinositide turnover in quartz-stimulated human polymorphonuclear leukocytes. Separation of inositol phosphates was carried out with a new ion-pair, reverse-phase high performance liquid chromatographic method applying a gentle tetrabutyl ammonium phosphate buffer gradient. The method separates inositol monophosphates, inositol 1,4-bisphosphate, inositol trisphosphates and inositol 1,3,4,5-tetrakisphosphate. Reactive oxygen metabolites, indices for leukocyte activation, were measured with a luminometric assay. Quartz increased the production of reactive oxygen metabolites, preceded by facilitated inositol phosphate turnover. This finding provides evidence that inositol phosphate second messengers may be involved in quartz-induced leukocyte activation and subsequent production of reactive oxygen metabolites.

Chromatography, High Pressure Liquid↗

Amplified detection of telomerase activity using electrochemical and quartz crystal microbalance measurements.

Telomerase is considered as an important biomarker for cancer cells. Two different methods for the amplified electrochemical and microgravimetric quartz-crystal-microbalance detection of telomerase activity originating from HeLa cancer cells are described. One method involves the telomerization of a primer (1) linked to the electrode, in the presence of telomerase from HeLa cell extract and dNTP, followed by the hybridization of a biotin-labeled nucleic acid (2) that is complementary to the telomere repeat units. The subsequent binding of an avidin-alkaline phosphatase conjugate (3) that catalyzes the oxidative hydrolysis of 5-bromo-4-chloro-3-indolyl phosphate (4) results in the precipitation of the insoluble product (5) on the electrode. The second method involves the telomerization of the primer (1) associated with the electrode, in the presence of the telomerase-containing HeLa cell extract and the dNTP nucleotide mixture that includes biotin-labeled dUTP. The telomerization leads to the labeling of the telomeres with biotin labels. The association of the avidin-alkaline phosphatase conjugate (3) to the biotin labels results in the biocatalyzed transformation of (4) to (5) and the formation of a precipitate on the electrode or the Au-quartz crystal. As numerous precipitate molecules are formed as a result of the formation of a single telomere, the methods represent routes for the amplified detection of telomerase activity. The formation of the precipitate on the respective transducers is probed by following the changes in the electrode resistance using chronopotentiometry, or by following the frequency changes of the piezoelectric quartz crystals. The amount of precipitate generated on the electrodes is controlled by the concentration of the HeLa cancer cells. The methods enable the detection of telomerase activity that is extracted from 1000 HeLa cancer cells.

Biomarkers, Tumor↗

Determination of trace metallic impurities in high-purity quartz by ion chromatography.

A method has been developed for the determination of relevant trace impurities (alkali, alkaline and transition metals) in high purity quartz by ion-chromatography. In situ reagent (HF) purification and simultaneous sample dissolution was achieved in a multichannel vapour phase digestion assembly. Twenty-one samples can be digested at a time in this vapour phase system. Significant decrease in the process blank levels for all the analytes was observed. Drastic reduction (250 times) of NH4+ blank was achieved in the described vapour phase digestion, which enables the determination of trace concentration of sodium in high purity quartz. After volatilisation of the matrix and unreacted HF, the clear water leached solutions were injected into an ion-chromatograph equipped with conductivity detector for the determination of alkali and alkaline earth metals. In the case of transition metals, the trace residues were leached with 10 mM HCl and after separation on a mixed bed analytical column (IonPac CS5) were detected by spectrophotometry after post column derivatisation using 4-(2-pyridylazo)resorcinol (PAR). The accuracy of the result was checked by their comparison with those obtained by independent methods like inductively coupled plasma (ICP) MS and ICP atomic emission spectrometry. The achievable detection limits are between 0.4 ng/g (Li) and 22 ng/g (Mn). The application of the method to the determination of the above trace metals in two high-purity-grade quartz samples is demonstrated.

Chromatography, Liquid↗

Impedance analysis of an electrode-separated piezoelectric sensor as a surface-monitoring technique for gelatin adsorption on quartz surface.

The early events pertaining to gelatin adsorption and desorption onto quartz surfaces were studied, employing an electrode-separated piezoelectric sensor (ESPS). The adsorption of gelatin on a quartz crystal surface corresponds to a mass increase, which can be monitored in real time by the changes in the impedance parameters of the ESPS. It was shown that the adsorption of gelatin on a quartz surface is partly irreversible with respect to the dilution of the bulk phase. The observed adsorption kinetics is compatible with a mechanism that involves adsorption, desorption, and transformation from a reversible adsorption state to irreversible one. A progressive approach method was established to simulate the adsorption process. The adsorption densities and kinetic parameters in the early adsorption process were obtained from the responses of the ESPS in the adsorption process. The influence of pH and ionic strength was tested. A comparison with the Langmuir adsorption model was made.

Adsorption↗

Action mechanism of water soluble ethanol on phospholipid monolayers using a quartz crystal oscillator.

Interaction between phospholipid monolayers (dihexadecyl phosphate: DHP, dipalmitoyl phosphatidyl choline: DPPC) and water soluble ethanol has been studied using quartz crystal microbalance (QCM) method and quartz crystal impedance (QCI) method. The quartz crystal oscillator was attached horizontally on the DHP and DPPC monolayers that were formed on the water surface. At low concentration, increased ethanol concentration decreased the frequency for QCM and increased the resistance for QCI. Both frequency and resistance approached asymptotically to a saturation value. A further increase in ethanol concentration induced a sudden and discontinuous linear change (a decrease in frequency and an increase in resistance). Based on these results, we propose the following action mechanism of ethanol on phospholipid monolayers: at low concentration, the ethanol hydrates adsorb into the monolayer/water interface and saturate on the interface. The monolayer viscosity also increases with the adsorption of hydrates. A further increase in concentration causes multilayer formation of hydrates and/or penetration of hydrates into the monolayer core. The viscosity of the interfacial layer (monolayer and interfacial structured water) changes dramatically according to the action of ethanol hydrates.

Adsorption↗

Quartz stones: spurious or iatrogenic?

We describe 2 cases of spurious quartz-containing calculi; the first patient-driven and the second iatrogenic. An iatrogenic etiology can occur after the use of holmium:yttrium-aluminum-garnet laser energy because the fiber tip is composed of quartz. To make the diagnosis of a spurious stone, a high degree of suspicion is essential. A quartz stone should prompt the diagnosis of a factitious disorder in the absence of the appropriate surgical history. Psychological counseling and/or referral to a pain management clinic should be considered in such cases.

Citric Acid↗

Quartz and pneumoconiosis in coalminers.

In a routine survey of 623 miners in one colliery, 21 men, an unusually high number, showed radiological progression of simple pneumoconiosis in spite of generally low exposures to mixed coalmine dust. Comparison of the dust exposures of the 21 men with those of matched controls without pneumoconiosis showed highly significant differences in the proportion of quartz in the mixed dust to which they had been exposed. Quartz exposure may be an important factor in the development and rapid progression of coalworkers' pneumoconiosis. Some indication of the levels of quartz exposure which are likely to be hazardous is given.

Air Pollutants, Occupational↗

Significant differences in the cellular and molecular reactions of rat and hamster lung after quartz exposure.

Exposure of rats to high doses of quartz and other insoluble isometric particles can produce lung tumors. In contrast, after exposure of such particles in hamsters no tumor outcome has been observed. Recent studies have demonstrated that the tumorigenic effect of particles is closely linked to the induction of inflammatory processes and the subsequent formation and persistence of mutagenic oxidative DNA-modifications. Species-specific differences in sensitivity to particles should therefore be reflected in the molecular reaction of the lung cells. We exposed rats and hamsters to two different doses of quartz (0.3 mg, 1.2 mg/100 g body weight) by intratracheal instillation and characterized the dose-related pattern of pulmonary inflammation (neutrophil recruitment, TNF), toxicity (protein content, surfactant phospholipids), antioxidant defence (glutathione content), mutagenicity (8-oxoguanine, p53) and proliferation. Our results clearly demonstrate a significantly higher response of the rat to quartz exposure for all determined molecular and cellular parameters. Therefore the examination of these parameters in humans would contribute to the evaluation of the relevance of rats or hamsters as models to predict particle-induced human lung cancer risk.

Animals↗

Quartz tuning fork biosensor.

The use of quartz tuning forks for biosensor applications is investigated. The basis of the sensor is to coat the tuning fork surfaces with specific biomolecules and measure subsequent mass loading from the selective binding of complementary analytes. Two experimental set-ups are evaluated, direct mechanical excitation and self-excitation. Mechanical excitation is achieved by mounting the fork on a piezoelectric plate and it is found that the change in oscillation amplitude on adsorption can be monitored to give the change in mass. However, a major drawback is that the sensitivity is determined by the Q-factor, which varies significantly between different sensors and different experimental arrangements. In self-excitation mode, tuning fork motion is activated and detected by placing the fork within a tuned circuit. Using self-excitation mode, anti-human IgG modified tuning forks can sense the binding of human IgG in the range of 5-100 microg ml(-1). The significance of this study is that quartz tuning forks are routinely made using standard microfabrication process, thus suggesting the possibility of facile microfabrication of arrays of quartz sensors.

Audiometry↗

Optimisation of the enzyme-based determination of hydrogen peroxide using the quartz crystal microbalance.

The benzidines, 3,3'-diaminobenzidine (DAB), 3,3'-dimethoxybenzidine (DMOB) and 3,3',5,5'-tetramethylbenzidine (TMB) were enzymatically oxidised to detect hydrogen peroxide, using the quartz crystal. The oxidised product mainly remains in suspension, resulting in a limited quartz sensor signal. We have used two non-ionic surfactants, Tween 80 and Triton X-100 to interact with the oxidised amphiphilic products to increase their solubility and surface activity, and their ability to adsorb to the crystal surface. Tween 80 exhibits optimised response effects for DAB, DMOB and TMB at 0.012, 0.005, and 0.002% (v/v), respectively, whereas Triton X-100 is optimum at 0.1, 0.2, and 0.006% (v/v), respectively. As a result, we have improved the quartz crystal sensor sensitivity to peroxide. The use of Triton X-100 gave an improved response time.

Benzidines↗

Real-time evaluation of macromolecular surface modified quartz crystal resonant sensors under cryogenic stress for biological applications.

This study presents a novel auto-gain-control based quartz acoustic sensor technology capable of constant quartz crystal operation when cycled between ambient (22 degrees C) and cryogenic temperatures (-196 degrees C), afforded by direct exposure of crystals to bulk liquid nitrogen. The real-time frequency response profiles due to freeze-thaw cycling on crystals of differing surface finish and two model macromolecular surface coatings were studied in order to determine surface events such as water uptake. The quartz crystal surface finishes used were optically polished or lapped to one of two surface finishes. These were used as control native gold electrodes, and these surfaces were further coated with bovine serum albumin or the tri-block copolymer, poloxamer-188 as model macromolecular surface architectures. Crystals were snap frozen in liquid nitrogen and allowed to return to ambient temperature under controlled conditions. The processes of ice formation, thawing and evaporation were followed in real-time and comparisons were made between the test samples in order to assess the capability of this technique for sensing changes in surface characteristics such as the entrapment of water.

Biosensing Techniques↗

Quartz balance DNA sensor.

Single-strand DNA-containing thin films were deposited onto quartz oscillators by the Langmuir-Blodgett technique towards the realization of a device capable of sensing the presence of the complementary DNA sequences which hybridize with the immobilized ones. DNA, once complexed with aliphatic amines, appears as a monolayer in a single-stranded form by X-ray small angle scattering. A quartz nanobalance is then utilized to monitor mass increment related to specific hybridization with a complementary DNA probe. The crystal quartz nanobalance, capable of high sensitivity, indeed appears capable of obtaining a prototype of a device capable of sensing the occurrence of particular genes or sequences in the sample under investigation. The validity of the nanogravimetric assay was confirmed by independent fluorescence measurements utilizing DAPI and a CCD camera.

Biosensing Techniques↗

Isolated electrodeless high-frequency quartz crystal microbalance for immunosensors.

This paper presents a contactless technique to measure shear bulk wave resonance frequencies of an isolated quartz crystal in a flow cell. The line antenna placed outside the cell generates and detects the resonance frequencies in a wireless-electrodeless manner. It is revealed that this mechanism relies on the quasistatic electric field. A 0.3-mm-thick AT-cut quartz was used, and its overtone resonance frequencies up to 80 MHz were measured in liquids. Exact vibrational analysis was carried out for a triple-layered resonator system consisting of the adsorbed material layer, the electrode film, and the quartz plate. It predicts higher frequency sensitivity to the adsorbed material at higher modes when the electrode layer is removed. The 13th overtone (72-MHz resonance frequency) was used to detect human immunoglobulin G with concentrations between 0.1 and 20 microg/mL captured by protein A immobilized on one side of the crystal. The real-time measurement of the frequency response yielded the equilibrium constant KA=5.21 x 10(7) M(-1).

Biosensing Techniques↗

A novel method of immobilizing antibodies on a quartz crystal microbalance using plasma-polymerized films for immunosensors.

A novel method of immobilizing antibodies on quartz crystals for use in immunosensors was developed using an ethylenediamine plasma-polymerized film matrix. The films formed on the quartz crystals are extremely thin and homogeneous, and they incorporate amino groups. Sensors produced using this method are more reproducible from sample to sample and exhibit lower noise and higher sensitivity than sensors made using conventional immobilization methods, e.g., via polyethylenimine and (gamma-aminopropyl)trimethoxysilane. This is, to our knowledge, the first reported application of plasma-polymerized films to quartz crystal microbalance immunosensors. Results on orientation-controlled immobilization of anti-bodies, reusability and calibration tests are also presented.

Animals↗

Predicting the wettability of quartz surfaces exposed to dense nonaqueous phase liquids.

A model incorporating electrostatic and van der Waals forces was used to predict the wetting behavior of several systems containing a quartz surface, water, and a dense nonaqueous phase liquid (DNAPL). The disjoining pressure between the quartz/water and a water/DNAPL interface as a function of their separation was calculated from a full solution of the nonlinear Poisson-Boltzmann equation allowing for charge regulation. For the pH regime associated with a positive pressure barrier, the quartz surface was predicted to be water wetting. The model takes into account the charging behavior of an isolated DNAPL/water interface as inferred from electrophoretic mobility data. It provides excellent predictions for four coal tar and creosote samples tested, where the quartz was oil-wetting below pH 5 and water-wetting at higher pH values. In a fifth sample, the transition occurred above pH 7, which indicates that mechanisms other than electrostatic interaction control the wetting behavior in this sample.

Environmental Pollution↗

Adhesion kinetics of viable Cryptosporidium parvum oocysts to quartz surfaces.

The transport and deposition (adhesion) kinetics of viable Cryptosporidium parvum oocysts onto ultrapure quartz surfaces in a radial stagnation point flow system were investigated. Utilizing an optical microscope and an image-capturing device enabled real time observation of oocyst deposition behavior onto the quartz surface in solutions containing either monovalent (KCl) or divalent (CaCl2) salts. Results showed a significantly lower oocyst deposition rate in the presence of a monovalent salt compared to a divalent salt. With a monovalent salt, oocyst deposition rates and corresponding attachment efficiencies were relatively low, even at high KCl concentrations where Derjaguin-Landau-Verwey-Overbeek (DLVO) theory predicts the absence of an electrostatic energy barrier. On the other hand, in the presence of a divalent salt, oocyst deposition rates increased continuously as the salt concentration was increased over the entire range of ionic strengths investigated. The unusually low deposition rate in a monovalent salt solution is attributed to "electrosteric" repulsion between the Cryptosporidium oocyst and the quartz surface, most likely due to proteins on the oocyst surface that extend into the solution. It is further proposed that specific binding of calcium ions to the oocyst surface functional groups results in charge neutralization and conformational changes of surface proteins that significantly reduce electrosteric repulsion.

Animals↗

Reconstruction of pristine and hydrolyzed quartz surfaces.

Reconstruction of the most common pristine and hydrolyzed surfaces of quartz was investigated with periodic density functional theory calculations. Surface energies of reconstructed pristine faces, pertinent to quartz growth morphologies in melts, are found to range from 0.071 eV/A2 for the (101) surface to 0.139 eV/A2 for the (001) surface, and they increase as (101) < (102) < (112) < [(100), (111)] < (110) < (001). Four types of reconstruction reactions are observed: (1) formation of two-membered rings from vicinal silyl and siloxy sites, (2) formation of a pair of tricoordinated/unicoordinated oxygen atoms, (3) formation of three-membered rings, and (4) transformation of silanone sites into siloxane sites. The main features of reconstructed pristine quartz surfaces are two-membered rings formed from bridged siloxy and silyl sites on all investigated surfaces, a stable site complex with geminal positively charged tricoordinated and negatively charged unicoordinated oxygen atoms revealed on the (112) surface, and charged nonbridged siloxy/silyl sites, which are more stable than radical siloxy/silyl sites. Hydrolyzed surface energies range from -0.010 eV/A2 for the (001) surface to 0.002 eV/A2 for the (101) surface and increase as (001) < (110) < (102) < (111) < (100) < (112) < (101). The hydrolyzed surface stability is found to depend strongly on inter-site silanol hydrogen bonding. Observed networks of hydrogen bonds are important for interactions between silica surfaces and biomolecules in an aqueous environment.

Hydrolysis↗

A gas chromatography-quartz crystal microbalance for speciation of sulfur compounds in landfill gas.

A new method, based on separation with gas chromatography and detection with a quartz crystal microbalance, was used for the quantification of ethane-1-thiol, propane-1-thiol, ethyl methyl sulfide, propane-2-thiol, butane-2-thiol and butane-1-thiol. The analytical error, the analysis time and the general analytical performance are identical for gas chromatography-mass spectrometry (GC-MS) and gas chromatography-quartz crystal microbalance (GC-QCM). However, the GC-QCM method constitutes a low cost alternative to GC-MS for monitoring individual sulfur compounds in landfill gas. It is an easily assembled apparatus made with an injection device, a furnace, a column, a crystal cell and a quartz crystal.

Air Pollutants↗