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Boris Mizaikoff

Publications and source records attributed to Boris Mizaikoff.

At least 19 recordsLinked to original sources
PubMed2007

In-situ AFM studies of the phase-transition behavior of single thermoresponsive hydrogel particles.

The volume phase transition (VPT) behavior of individual thermally responsive poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) hydrogel microparticles was studied by in-situ dynamic mode atomic force microscopy (AFM) and force spectroscopy during heating and cooling cycles. Hydrogel samples were prepared by electrostatic immobilization of microparticles to amine-modified gold surfaces. The AFM studies of particle deswelling were performed by varying the force applied on the particles during imaging as a function of the geometry and material of the AFM probe. Aluminum-coated silicon cantilevers were found to influence substantially the behavior of the particles during the VPT, leading to a significant shape change. Low force impact magnetic excitation of the AFM probe (MAC mode) during dynamic mode measurements resulted in an undisturbed deswelling behavior enabling observation of the expected volume changes of the particles without significant tip-sample interaction. Hence, MAC-mode AFM was determined to be the most suitable technique for in-situ AFM studies on volume and shape changes at single hydrogel particles during VPT. Elasticity measurements performed at single particles at temperatures below and above the VPT revealed a 15-fold increase in the Young's modulus after passing the VPT, indicating the transition from a soft, swollen network to a stiffer, deswollen state.

Acrylamides↗
PubMed2006

Imprinted polymeric materials. Insight into the nature of prepolymerization complexes of quercetin imprinted polymers.

Molecular imprinting techniques have proved to be a highly accessible method for producing molecule-specific recognition materials for a variety of applications, ranging from sensing to catalysis and separations. In noncovalent imprinting, it is anticipated that polymerizable complexes are created in the prepolymerization solution via self-assembly of functional monomers and template molecules resulting from inherent chemical complementarity, which will ideally form binding sites within the cross-linked matrix after polymerization. On the basis of 1H NMR data and X-ray crystallographic evidence, we now infer a more important role for template self-association for the recognition properties of quercetin-imprinted polymers. While directly applicable to fundamental understanding of the molecular imprinting mechanism of this polyphenol, on a more generic scale, this work also demonstrates the utility of this strategy toward analyzing complex noncovalent interaction mechanisms between small molecules. These interactions are of particular interest for quercetin and other members of the flavone/flavonoid class of compounds, which are radical-scavenging polyphenols of substantial interest to biomedicine.

Journal Article↗
PubMed2006

Fabrication and characterization of molecular beam epitaxy grown thin-film GaAs waveguides for mid-infrared evanescent field chemical sensing.

Thin-film GaAs waveguides were designed and fabricated by molecular beam epitaxy for use in mid-infrared (MIR) evanescent field liquid sensing. Waveguides were designed to facilitate the propagation of a single mode at a wavelength of 10.3 microm emitted from a distributed feedback quantum cascade laser, which overlaps with molecular selective absorption features of acetic anhydride. The characterization of the waveguides shows transmission across a broad MIR band. Evanescent field absorption measurements indicate a significant sensitivity enhancement in contrast to multimode planar silver halide waveguides.

Equipment Design↗
PubMed2006

Label-free DNA detection based on modified conducting polypyrrole films at microelectrodes.

A label-free electrochemical detection method for DNA hybridization based on electrostatic modulation of the ion-exchange kinetics of a polypyrrole film deposited at microelectrodes is reported. Synthetic single-stranded 27-mer oligonucleotides (probe) have been immobilized at 2,5-bis(2-thienyl)-N-(3-phosphorylpropyl)pyrrole film formed by electropolymerization on the previously formed polypyrrole layer. The 27- or 18-mer target oligonucleotides were monitored via the electrochemically driven anion exchange of the inner polypyrrole film. The performance of the miniaturized DNA biosensor system was studied in respect to selectivity, sensitivity, reproducibility, and regeneration of the sensor. Control experiments were performed with a noncomplementary target of 27-mer DNA and 12 base-pair mismatched 18-mer sequences, respectively, and did not show any unspecific binding. Under optimized experimental conditions, the label-free electrochemical biosensor enabled the detection limits of 0.16 and 3.5 fmol for the 18- and 27-mer DNA strand, respectively. Furthermore, we demonstrate reusability of the electrochemical DNA biosensor after successful recovery of up to 100% of the original signal by regenerating the DNA "label-free" electrode with 50 mM HCl at room temperature.

Base Sequence↗
PubMed2006

Real-time fourier transform-infrared analysis of carbon monoxide and nitric oxide in sidestream cigarette smoke.

Fourier transform infrared (FT-IR) spectroscopy was compared directly to independent standard analytical techniques for the routine measurement of carbon monoxide (CO) and nitric oxide (NO) yields from cigarette sidestream smoke. The FT-IR instrument was configured in-line with a nondispersive infrared (NDIR) analyzer for CO analysis and a chemiluminescence (CL) analyzer for NO analysis to monitor the sidestream smoke from a single port of a linear smoking machine. A cold trap was inserted prior to the FT-IR to minimize the levels of vapor phase interferents, such as water. Univariate and multivariate regression analysis were evaluated for the prediction of cigarette yield from time-resolved spectral data at 1, 2, 4 and 8 cm-1 spectral resolution. Regressions were developed using three different spectral ranges including unique rotation-vibration lines, the R-branch, and the entire absorption band. As per standard methods, yields were calculated from the concentration traces generated during the smoke runs for five different cigarettes spanning the expected range of mainstream total particulate matter deliveries. The FT-IR traces for the smoke runs revealed improved temporal resolution yielding analytical information from smoke generated in between puffs. The performance between the validation methods and the FT-IR calibrations was statistically compared. In general, for the determination of CO, the FT-IR calibrations underestimated the yield measured by NDIR by less than 10%. For the NO measurement, the univariate FT-IR calibrations overestimated the NO yield measured by the CL analyzer, whereas the partial least squares (PLS) calibrations showed good agreement. PLS calibrations were developed for both analytes providing no significant difference when compared to the respective standard analytical techniques. Results for sidestream CO and NO yields for Kentucky reference cigarette 1R4F utilizing 8 cm-1 calibrations compared favorably to values reported elsewhere in the literature. Hence, calibration of the FT-IR system at 8 cm-1 spectral resolution clearly revealed the potential of this method, providing enhanced temporal resolution, simultaneous determination of several smoke components, and reduced complexity of the experimental setup in contrast to the standard techniques.

Air Pollutants↗
PubMed2006

Characterization of a mid-infrared hollow waveguide gas cell for the analysis of carbon monoxide and nitric oxide.

Infrared spectroscopy is commonly applied to the analysis of small gas-phase molecules. One of the limitations of using Fourier transform infrared (FT-IR) spectroscopy for these applications is the time response of long path length gas cells. Hollow waveguides (HW) that transmit in the mid-infrared spectral range have higher optical efficiencies compared to long path length cells due to smaller cell volumes. This study characterizes a silver coated, 2 mm inner diameter HW for the analysis of carbon monoxide (CO) and nitric oxide (NO) and compares the performance to a 3 m gas cell and traditional gas analyzers. The HW was found to have a CO response time less than the NDIR analyzer and approximately one-tenth of the response time on the FT-IR system equipped with a 3 m gas cell. The utility of the increased response time was demonstrated by measuring CO concentrations in sidestream cigarette smoke at the same temporal resolution as an NDIR analyzer. A 10 to 60% increase in sensitivity using various frequencies for both CO and NO was observed using the HW compared to the 3 m multipass gas cell. However, cost savings for gas-sensing applications can be achieved on a per analyte basis by using FT-IR spectroscopy, especially in combination with a HW gas-sensing module, which is significantly less expensive than a multipass gas cell.

Air Pollutants↗
PubMed2006

Shining new light on old principles: localization of evanescent field interactions at infrared-attenuated total reflection sensing interfaces.

A combined experimental and spectral ray tracing approach for identifying and evaluating evanescent field interactions with discrete surface deposits along a horizontal attenuated total reflection (HATR) element is presented. By experimentally depositing poly(styrene-co-butadiene) (PSCB) residues at fixed intervals along the measurement surface of a HATR crystal, distinct regions of evanescent field interaction with the surface deposits along the multi-reflection waveguide are visualized via infrared absorption features of PSCB. The infrared-attenuated total reflection (IR-ATR) measurements were confirmed by spectral ray tracing analysis simulating transmission-absorption spectra after modeling the polymeric surface deposits as thin-film IR absorbing cylinders. The presented analytical procedures and simulations provide a generic strategy for identifying and evaluating "active" sensing regions along ATR elements. Additionally, the simulated ATR setup along with the presented spectral ray tracing procedures provide a virtual platform aiding the development, optimization, and integration of deep-sea IR-ATR sensor probes with submersible mid-infrared spectrometers for in situ marine monitoring applications, which was the initial motivation for these studies.

Algorithms↗
PubMed2006

Classification of atherosclerotic rabbit aorta samples with an infrared attenuated total reflection catheter and multivariate data analysis.

The strongly overlapping infrared absorption features of atherosclerotic and normal rabbit aorta samples as governed by their water, lipid, and protein content render the direct evaluation of molecular characteristics obtained from infrared (IR) spectroscopic measurements challenging for classification. We have successfully applied multivariate data analysis and classification techniques based on partial least squares regression (PLS), linear discriminant analysis (LDA), and principal component regression (PCR) to IR spectroscopic data obtained by using a recently developed infrared attenuated total reflectance (IR-ATR) catheter prototype for future in vivo diagnostic applications. Training data were collected ex vivo from atherosclerotic and normal rabbit aorta samples. The successful classification results on atherosclerotic and normal aorta samples utilizing the developed data evaluation routines reveals the potential of spectroscopy combined with multivariate classification strategies for the identification of normal and atherosclerotic aorta tissue for in vitro and, in the future, in vivo applications.

Algorithms↗
PubMed2005

Molecularly imprinted micro and nanospheres for the selective recognition of 17beta-estradiol.

A one-step precipitation polymerization procedure for the synthesis of molecularly imprinted polymers selective for 17beta-estradiol yielding imprinted micro and nanospheres was developed in this study and compared to templated materials obtained by conventional bulk polymerization. The polymer particles prepared by precipitation polymerization exhibited a regular spherical shape at the micro and nanoscale with a high degree of monodispersity. Moreover, the influence of the polymerization temperature, and the ratio of functional monomer to cross-linker on the size of the obtained particles was investigated. The selectivity of the imprinted micro and nanospheres was evaluated by HPLC analysis and via radioligand binding assays. HPLC separation experiments revealed that the imprinted microspheres provide higher or similar affinity to the template in contrast to imprinted polymers prepared by conventional bulk polymerization or synthesized by multi-step swelling/polymerization methods. The dimensions of the imprinted nanospheres facilitate suspension in solution rendering them ideal for binding assay applications. Results from saturation and displacement assays prove that the imprinted nanospheres exhibit superior specific affinity to the target molecule in contrast to control materials. The binding properties of the nanospheres including binding isotherms and affinity distribution were studied via Freundlich isotherm affinity distribution (FIAD) analysis. Moreover, release experiments show that 70% of rebound 17beta-estradiol was released from the imprinted nanospheres within the first 2 h, while more intimately bound 17beta-estradiol molecules (approx. 16%) were released in the following 42 h. Fitting Brunnauer-Emmet-Teller (BET) multi-point adsorption isotherms to the obtained results indicated that the micro and nanospheres are characterized by a comparatively homogenous and narrow distribution of mesopores in contrast to the corresponding bulk polymers.

Biosensing Techniques↗
PubMed2005

Analyzing the mechanisms of selectivity in biomimetic self-assemblies via IR and NMR spectroscopy of prepolymerization solutions and molecular dynamics simulations.

Molecularly imprinted polymers (MIPs) for 2,4-dichlorophenoxyacetic acid were synthesized via a noncovalent approach with 4-vinylpyridine as functional monomer and ethylene glycol dimethacrylate as cross-linker in a methanol/water mixture. Templated polymers synthesized in this self-assembly approach rely on complex formation between the target analyte and functional monomers in porogenic solution prior to radical polymerization. Consequently, the achievable selectivity is governed by the nature and stability of these complexes. The nature of noncovalent interactions responsible for complex formation during imprinting of the template 2,4-dichlorophenoxyacetic acid (2,4-D) with the functional monomer 4-vinylpyridine has been investigated. Fourier transform infrared and 1H NMR spectroscopies provide the fundamental analytical basis for rationalizing the mechanisms of recognition during the imprinting process probing the governing interactions for selective binding site formation at a molecular level. Molecular modeling studies in explicit solvent (chloroform and water) corroborate the importance of hydrogen bonding in aprotic solvents and of hydrophobic interactions in protic media in agreement with the experimental spectroscopic investigations of prepolymerization solutions. Furthermore, chromatographic studies of the synthesized MIPs provided insight on the importance of size, shape, and functionality during selective 2,4-D rebinding processes confirming the results obtained during the prepolymerization studies.

Journal Article↗
PubMed2005

Infrared evanescent field sensing with quantum cascade lasers and planar silver halide waveguides.

We demonstrate the first midinfrared evanescent field absorption measurements with an InGaAs/AlInAs/InP distributed feedback (DFB) quantum cascade laser (QCL) light source operated at room temperature coupled to a free-standing, thin-film, planar, silver halide waveguide. Two different analytes, each matched to the emission frequency of a QCL, were investigated to verify the potential of this technique. The emission of a 1650 cm(-1) QCL overlaps with the amide absorption band of urea, which was deposited from methanol solution, forming urea crystals at the waveguide surface after solvent evaporation. Solid urea was detected down to 80.7 microg of precipitate at the waveguide surface. The emission frequency of a 974 cm(-1) QCL overlaps with the CH3-C absorption feature of acetic anhydride. Solutions of acetic anhydride in acetonitrile have been detected down to a volume of 0.01 microL (10.8 microg) of acetic anhydride solution after deposition at the planar waveguide (PWG) surface. Free-standing, thin-film, planar, silver halide waveguides were produced by press-tapering heated, cylindrical, silver halide fiber segments to create waveguides with a thickness of 300-190 microm, a width of 3 mm, and a length of 35 mm. In addition, Fourier transform infrared (FT-IR) evanescent field absorption measurements with planar silver halide waveguides and transmission absorption QCL measurements verify the obtained results.

Journal Article↗
PubMed2005

Numerical simulation of scanning electrochemical microscopy experiments with frame-shaped integrated atomic force microscopy--SECM probes using the boundary element method.

Integrated submicroelectrodes for combined AFM-SECM measurements are characterized with numerical simulations using the boundary element method. SECM approach curves and SECM images are calculated and analyzed for a model substrate containing pronounced topographical and electrochemical features. The theoretically calculated image has been compared to the experimental data and shows excellent quantitative agreement. Hence, the applicability of integrated AFM-SECM electrodes for combined electrochemical and topographical imaging and a profound theoretical description including quantification of the obtained results are demonstrated.

Electrochemistry↗
PubMed2005

Molecularly imprinted polymers for biomolecular recognition.

Molecular imprinting of polymers is a concept for the synthetic formation of structurally organized materials providing binding sites with molecular selectivity. Compared to biological receptors, these polymeric recognition systems have the advantage of superior chemical and mechanical stability with potential applications in areas such as biomimetic catalysis and engineering, biomedical analysis, sensor technology, or the food industry. In particular, molecularly imprinted polymers (MIPs) providing selectivity for biorelated molecules are gaining substantial importance. In this context, a self-assembly approach for the synthesis of imprinted polymers against the flavonol quercetin is presented, which is exemplary for the biologically relevant group of flavonoid compounds. The creation of synthetic selective recognition sites for this biomolecule is demonstrated by comparing the separation capabilities of imprinted and nonimprinted polymer particles for several structurally related molecules via high-performance liquid chromatography experiments. The developed quercetin-MIP enables selective extraction of quercetin even from complex mixtures, demonstrating the potential for designing biomimetic recognition materials with improved selectivity for biomolecules with tunable functionality at a nanoscale.

Chemistry Techniques, Analytical↗
PubMed2005

Nanoelectrodes integrated in atomic force microscopy cantilevers for imaging of in situ enzyme activity.

For investigation of laterally resolved information on biological activity, techniques for simultaneously obtaining complementary information correlated in time and space are required. In this context, recent developments in scanning probe microscopy are aimed at information on the sample topography and simultaneously on the physical and chemical properties at the nanometer scale. With the integration of submicro- and nanoelectrodes into atomic force microscopy (AFM) probes using microfabrication techniques, an elegant approach combining scanning electrochemical microscopy with AFM is demonstrated. This instrumentation enables simultaneous imaging of topography and obtainment of laterally resolved electrochemical information in AFM tapping mode. Hence, topographical and electrochemical information on soft surfaces (e.g., biological species) and polymers can be obtained. The functionality of tip-integrated electrodes is demonstrated by simultaneous electrochemical and topographical studies of an enzyme-modified micropattern.

Enzymes↗
PubMed2004

Imaging of ATP membrane transport with dual micro-disk electrodes and scanning electrochemical microscopy.

Extracellular adenosine-5'-triphosphate (ATP) is involved in a variety of relevant regulatory mechanisms at a cellular level and has therefore been focus of extensive research. One of the major challenges associated with measuring this key regulatory analyte is the ability to detect and localize extracellular ATP with sufficient spatial and temporal resolution in physiological environments. In this study, scanning electrochemical microscopy (SECM) utilizing an amperometric micro-biosensor based on co-immobilization of the enzymes glucose oxidase and hexokinase is applied for imaging ATP transport through a porous polycarbonate membrane under physiologically relevant conditions. The enzymatic biosensor operates on competitive consumption of the substrate glucose between the immobilized enzymes glucose oxidase and hexokinase involving ATP as a co-substrate. Quantitative determination of the ATP concentration is based on a linear correlation between the glucose consumption and the ATP level. Integration of the amperometric ATP micro-biosensor into a dual micro-disk electrode configuration is achieved by immobilizing the enzymes at one of the micro-disk electrodes while the second disk serves as an unmodified amperometric probe for controlled positioning of the micro-biosensor in close proximity to the sample surface enabling quantification of the obtained current signal.

Adenosine Triphosphate↗
PubMed2004

Analysis of corrosion processes at the surface of diamond-like carbon protected zinc selenide waveguides.

A detailed surface analytical study on the corrosion behavior of unprotected and diamond-like carbon (DLC)-coated mid-infrared (MIR) waveguides used in remote sensing applications at strongly oxidizing conditions is presented. High-quality DLC films, with a thickness of 100 nm serving as MIR-transparent corrosion barrier, have been produced at the surface of zinc selenide (ZnSe) attenuated total reflection waveguides via pulsed laser deposition techniques. IR microscopy and atomic force microscopy are applied to investigate the chemical inertness of DLC-based membranes against aqueous solutions of hydrogen peroxide. These stability studies show that uncoated ZnSe waveguides are subject to severe chemical surface modifications, while DLC-protected waveguides maintain their optical properties and chemical integrity. In situ studies on the corrosion behavior by a recently developed approach combining scanning electrochemical microscopy (SECM) with Au/Hg amalgam ultramicroelectrodes in a scanning stripping voltammetry experiment provides additional insight into the mechanisms of the corrosion process. It is demonstrated that the combination of surface analytical techniques and, in particular, the innovative application of SECM with amalgam electrodes provides superior information on corrosion processes at the surface of optical waveguides. This detailed study confirms the efficiency of protective DLC coatings deposited onto IR-transparent optical waveguides, rendering this novel concept ideal for sensing applications in harsh environments.

Journal Article↗
PubMed2004

Amperometric ATP biosensor based on polymer entrapped enzymes.

A dual enzyme electrode for the detection of adenosine-5'-triphosphate (ATP) at physiologically relevant pH levels was developed by co-immobilization of the enzymes glucose oxidase (GOD) and hexokinase (HEX) using pH-shift induced deposition of enzyme containing polymer films. Application of a simple electrochemical procedure for the co-immobilization of the enzymes at electrode surfaces exhibits a major improvement of sensitivity, response time, reproducibility, and ease of fabrication of ATP biosensors. Competition between glucose oxidase and hexokinase for the substrate glucose involving ATP as a co-substrate allows the determination of ATP concentrations. Notable control on the immobilization process enables fabrication of micro biosensors with a diameter of 25 microm. The presented concept provides the technological basis for a new generation of fast responding, sensitive, and robust biosensors for the detection of ATP at physiological pH values with a detection limit of 10 nmol l(-1).

Adenosine Triphosphate↗