PubMed Health⌕ Search

Biomedical subjects

Boris Mizaikoff

Publications and source records attributed to Boris Mizaikoff.

31 records · Page 2Linked to original sources
PubMed2004

Scanning electrochemical microscopy imaging of rhodochrosite dissolution using gold amalgam microelectrodes.

Gold/mercury amalgam (Au/Hg) microelectrodes with a diameter of 25 microm were developed for the detection of environmentally relevant analytes such as manganese and iron by scanning electrochemical microscopy (SECM), and applied to investigate the controlled dissolution of manganese carbonate (MnCO(3); rhodochrosite) in acidic conditions. Characterization of the amalgam electrode geometry via approach curves recorded during SECM experiments revealed Au/Hg microelectrodes with sphere cap geometry. Quantitative determination of Mn(2+) has been achieved by calibration of the Au/Hg microelectrode in bulk solution experiments. Subsequent SECM imaging experiments confirm the applicability of amalgam microelectrodes for imaging of Mn(2+) production during dissolution of MnCO(3) at pH 3.9. This study confirms feasibility and provides the fundamental basis of SECM imaging with amalgam microelectrodes to address biogeochemically relevant questions.

Electrochemistry↗
PubMed2004

Combination of sorption tube sampling and thermal desorption with hollow waveguide FT-IR spectroscopy for atmospheric trace gas analysis: determination of atmospheric ethene at the lower ppb level.

The determination of organic trace gases in the ambient environment at the lower ppb level is demonstrated based on a novel technique combining sorption tube sampling on Molsieve and Carbosieve S-III, thermal desorption, and detection of the trace analyte by hollow waveguide Fourier transform infrared (HWG-FT-IR) spectroscopy. While ethene concentrations of approximately 5 ppm can be directly observed using HWG-FT-IR, enrichment factors of up to 5000 were achieved by sorption tube sampling and thermal desorption. Detection limits of approximately 1 ppb are reported. Efficient enrichment by the sampling tube is achieved due to the favorable internal volume ( approximately 0.4 cm(3) at a length of 470 mm) of the hollow waveguide serving as a miniaturized gas cell. This new method was validated for ethene by thermodesorption-cryofocusing-GC-FID as the reference method. Analytical performance has been compared for standard gas mixtures and for ethene measurements in urban air. Finally, ethene data from a sampling campaign at two alpine sites in Tyrol/Austria are presented.

Journal Article↗
PubMed2004

Direct analysis of oxidizing agents in aqueous solution with attenuated total reflectance mid-infrared spectroscopy and diamond-like carbon protected waveguides.

A novel approach for the direct detection of oxidizing agents in aqueous solution is presented using diamond-like carbon (DLC) protected waveguides in combination with attenuated total reflectance (ATR) mid-infrared spectroscopy. Pulsed laser deposition was applied to produce high-quality DLC thin films on ZnSe ATR crystals with thicknesses of a few 100 nm. Scanning electron microscopy and X-ray photoelectron spectroscopy has been used to investigate the surface properties of the DLC films including the sp(3)/sp(2) hybridization ratio of the carbon bonds. Beside excellent adhesion of the DLC coatings to ZnSe crystals, these films show high chemical stability against strongly oxidizing agents. IR microscopy was utilized to compare differences in the chemical surface modification of bare and protected ATR waveguides when exposed to hydrogen peroxide, peracetic acid, and peroxydisulfuric acid. The feasibility of DLC protected waveguides for real-time concentration monitoring of these oxidizing agents was demonstrated by measuring calibration sets in a concentration range of 0.2-10%. Additionally, principal component regression has been applied to analyze multicomponent mixtures of hydrogen peroxide, acetic acid, and peracetic acid in aqueous solution. Due to high chemical stability and accurate monitoring capabilities, DLC protected waveguides represent a novel approach for directly detecting oxidizing agents in aqueous solution with promising potential for industrial process analysis.

Journal Article↗
PubMed2004

Chemometric correction of drift effects in optical spectra.

All quantitative data evaluation techniques applied to spectroscopy are based on the assumption that the baseline is stable in time. If this prerequisite is violated, major concentration errors can result since drifts are evaluated along with true spectroscopic features. For handling baseline drifts two improved principal component regression (PCR) methods are presented and compared to conventional Savitzky-Golay preprocessing followed by conventional PCR. The proposed drift-correction methods take advantage of baseline drifts being rather broad compared to the absorption features. The only assumption made is that drift effects can be modeled sufficiently by polynomials of user-selectable order. One correction method modifies principal components such that drifts of polynomial shape are orthogonal to the calibration model and thus cannot influence the concentration result. The second method extends the calibration model by synthetic so-called pseudo-principal components. While the principal components model the true spectral features, the pseudo-principal components describe drifts simultaneously and independently. Hence, drifts are explicitly included into the calibration and cannot cause erroneous concentration results. It is demonstrated that both correction methods are equivalently as powerful as the conventional PCR in the absence of drifts and superior if drifts are present. The overall performance--in the absence and presence of baseline drifts--of the novel methods makes them more versatile and reliable than the conventional Savitzky-Golay data preprocessing. In almost all investigated cases, the average concentration errors were significantly smaller than those obtained by Savitzky-Golay preprocessing. Furthermore, polyPCR and pPCR do not need laborious optimizations as Savitzky-Golay does for preventing suppression of relevant signal components. polyPCR demands less computation expense than Savitzky-Golay, and pPCR extracts the drift spectrum as additional qualitative information not provided by Savitzky-Golay.

Algorithms↗
PubMed2003

Introduction and application of secured principal component regression for analysis of uncalibrated spectral features in optical spectroscopy and chemical sensing.

In this study, a novel chemometric algorithm for improved evaluation of analytical data is presented and applied to three spectroscopic data sets obtained by different analytical methods. This so-called secured principal component regression (sPCR) was developed for detecting and correcting uncalibrated spectral features newly emerging in spectra after finalizing the PCR calibration, which may result in major concentration errors. Hence, detection and correction of uncalibrated features is essential. Furthermore, detected uncalibrated features provide qualitative information for sensing and process monitoring applications indicating problems in the process flow. After conventional PCR calibration, sPCR analyzes measurement data in two steps: The first step investigates whether the obtained data set is consistent with the calibration model or not. If spectroscopic features are found that cannot be modeled by the principal components, they are extracted from the measurement spectrum. This corrected spectrum is then evaluated by conventional PCR. In the Experimental Section, sPCR was successfully applied to three data sets obtained by different spectroscopic measurements in order to corroborate general applicability of the proposed concept. For each data set, one of several substances was excluded from the calibration acting in the sPCR assessment as uncalibrated absorber. The test sets consisted of disturbed and undisturbed samples. A total of 109 out of 110 test samples were correctly classified as disturbed or undisturbed by an uncalibrated absorber. It was confirmed that the extracted disturbance spectra are in accordance with the spectra of the uncalibrated analytes. The concentration results obtained with sPCR were found to be equivalent to conventional PCR results in the case of undisturbed samples and more precise for disturbed samples.

Journal Article↗
PubMed2003

Model-based optimal design of polymer-coated chemical sensors.

A model-based methodology for optimal design of polymer-coated chemical sensors is developed and is illustrated for the example of infrared evanescent field chemical sensors. The methodology is based on rigorous and computationally efficient modeling of combined fluid mechanics and mass transfer, including transport of multiple analytes. A simple algebraic equation for the optimal size of the sensor flow cell is developed to guide sensor design and validated by extensive CFD simulations. Based upon these calculations, optimized geometries of the sensor flow cell are proposed to further improve the response time of chemical sensors.

Journal Article↗
PubMed2003

Application of mid-infrared spectroscopy: measuring hydrogen peroxide concentrations in bleaching baths.

The presented work applies mid-infrared attenuated total reflection (ATR) spectroscopy to the measurment of hydrogen peroxide in aqueous matrices. The performance of different ATR crystals mounted in flow cells was investigated in the presence of aqueous hydrogen peroxide solutions. Quantitative determination has been achieved by evaluation of specific OH stretching and deformation vibrations with linear correlation between peak areas or peak heights and hydrogen peroxide concentration in the range of 1-10% (weight in water). Important aspects such as chemical stability of the waveguide material and influences of pH and ionic strength on the performance are discussed. Feasibility for the investigation of real world samples is demonstrated by measuring industrial bleaching solutions with known concentrations of hydrogen peroxide fitting well with calibration graphs established with neat hydrogen peroxide solutions. The presented sensor system is capable of determining hydrogen peroxide within complex matrices and clearly corroborates the potential of providing an in situ measurement concept for on-line hydrogen peroxide detection.

Hydrogen Peroxide↗
PubMed2003

New frontiers for mid-infrared sensors: towards deep sea monitoring with a submarine FT-IR sensor system.

A sub-sea deployable fiber-optic sensor system for the continuous determination of a range of environmentally relevant volatile organic compounds in seawater has been developed. The prototype of a robust, miniaturized Fourier transform infrared (FT-IR) spectrometer for in situ underwater pollution monitoring was designed, developed, and built in our research group. The assembled instrument is enclosed in a sealed aluminium pressure vessel and is capable of maintenance-free operation in an oceanic environment down to depths of at least 300 m. The whole system can be incorporated either in a tow frame or a remotely operated vehicle (ROV). A suitable fiber-optic sensor head was developed, optimized in terms of sensitivity and hydrodynamics, and connected to the underwater FT-IR spectrometer. Due to a modular system design, various other sensor head configurations could be realized and tested, ensuring facile adaptation of the instrument to future tasks. The sensor system was characterized in a series of laboratory and simulated field tests. The sensor proved to be capable of quantitatively detecting a range of chlorinated hydrocarbons and monocyclic aromatic hydrocarbons in seawater down to the low ppb (microg/L) concentration range, including mixtures of up to 6 components. It has been demonstrated that varying amounts of salinity, turbidity, or humic acids, as well as interfering seawater pollutants, such as aliphatic hydrocarbons or phenols, do not significantly influence the sensor characteristics. In addition, the sensor exhibits sufficient long-time stability and a low susceptibility to sensor fouling.

Equipment Design↗
PubMed2003

Development and optimization of a mid-infrared hollow waveguide gas sensor combined with a supported capillary membrane sampler.

A gas sensor for application in water analysis was developed by combination of a mid-infrared (MIR) hollow waveguide with a Fourier transform infrared (FT-IR) spectrometer and coupling of the hollow waveguide gas sensor module to a supported capillary membrane sampler (SCMS) for continuous liquid-gas extraction. Different hollow waveguides have been characterized in this study for developing an optimized optical configuration. Analysis of industrially relevant compounds has been performed, investigating chlorinated hydrocarbons (CHCs), such as dichloromethane and chloroform, representing highly volatile analytes, and 1,4-dioxane as an example of target compounds with low volatility. The suitability of this spectroscopic IR sensing system for industrial applications is demonstrated under simulated real-world conditions with limits of detection in the ppb (v/v) and ppm (v/v) concentration range for CHCs and 1,4-dioxane, respectively.

Dioxanes↗
PubMed2003

Sol-gel-coated mid-infrared fiber-optic sensors.

Application of organically modified sol-gels as novel recognition membranes for mid-infrared fiber-optic sensors is demonstrated for the first time by in situ detection of nitro-based aromatic compounds in aqueous media. Sol-gels were prepared by acid- and base-catalyzed copolymerization of alkyltrimethoxysiloxanes and applied onto the surface of silver halide (AgCl(0.3)Br(0.7)) fibers by drip coating. The coating process was monitored in situ using Fourier transform infrared (FT-IR) spectroscopy. Homogeneity of the layers was analyzed by scanning electron microscopy. Sol-gel-coated evanescent held sensors were investigated with respect to their capacity to suppress interfering water background absorptions, repeatability of dissolved analyte enrichment, and sensor response time. Nitrobenzene and parathion are the investigated analytes; figures of merit are derived from calibration curves determined to assess sensitivity and reproducibility of the developed sensor system. It can be concluded that sol-gel-coated infrared fiber-optic sensors enable reproducible detection of nitro-based aromatic compounds in the low ppm concentration range. Due to wide flexibility in tuning chemical properties of sol-gel films along with superior mechanical and chemical stability, organically modified sol-gels represent highly interesting coating materials for mid-infrared sensing applications.

Calibration↗
PubMed2002

Advanced solid phase extraction using molecularly imprinted polymers for the determination of quercetin in red wine.

Solid phase extraction (SPE) based on molecularly imprinted polymers (MIPs) is a novel approach for sample preparation and preconcentration, gaining increased interest in the fields of environmental, clinical, and food analysis. The first application combining MIPs with SPE for advanced beverage analysis is reported. MIPs for the flavonoid quercetin have been generated, using quercetin as a template molecule in a self-assembly approach and yielding imprinting of 1% of the used template. The MIP achieved a capacity of 0.4 g quercetin per gram polymer and a recovery rate of 98.2%. The application of these synthetic receptors as SPE material for the selective extraction and preconcentration of quercetin from synthetic and red wine samples was investigated. Red wine samples from a French Merlot were directly applied onto the SPE cartridge. The collected fractions were analyzed by high-pressure liquid chromatography. For verification of the obtained results, a similarly prepared nonimprinted polymer and a classical octadecyl silane reversed-phase cartridge were applied as the SPE matrix during control experiments. The MIP enabled the selective extraction of quercetin from a complex matrix, such as red wine, spiked with 8.8 mg per liter quercetin, demonstrating the potential of molecularly imprinted solid phase extraction for rapid, selective, and cost-effective sample pretreatment.

Acetonitriles↗