TY - GEN A1 - Delaney, Tetyana L. A1 - Zimin, Denys A1 - Rahm, Michael A1 - Weiss, Dieter A1 - Wolfbeis, Otto S. A1 - Mirsky, Vladimir M. T1 - Capacitive detection in ultrathin chemosensors prepared by molecularly imprinted grafting photopolymerization T2 - Analytical Chemistry N2 - The usual applications of capacitive detection in chemo- and biosensors are based on changes in effective thickness of insulating layers due to adsorption of analyte onto receptors. Ultrathin chemosensors based on molecularly imprinted polymerization enable a realization of another capacitive approach that exploits changes in electrical capacitance due to modification of the dielectric constant of the polymer. Such chemosensors were prepared by photografted molecularly imprinted polymerization on the surface of gold electrodes. An adsorbed layer of hydrophobic photoinitiator (benzophenone) provided grafted polymerization on the surface of the alkanethiol-modified gold electrode. The chemosensors were characterized by cyclic voltammetry, impedance spectroscopy, and scanning electron and atomic force microscopy. Binding of analyte was detected by measurements of electrical capacitance. The results indicate a decrease of the dielectric constant of the polymer layer due to analyte binding up to 20%. Y1 - 2007 U6 - https://doi.org/10.1021/ac062143v SN - 0003-2700 SN - 1520-6882 VL - 79 IS - 8 SP - 3220 EP - 3225 ER - TY - CHAP A1 - Mirsky, Vladimir M. ED - Corain, Benedetto ED - Schmid, Günter ED - Toshima, Naoki T1 - Spreader-bar structures as molecular templates for electrochemical synthesis of nanoparticles T2 - Metal nanoclusters in catalysis and materials science: the issue of size-control Y1 - 2008 U6 - https://doi.org/10.1016/B978-044453057-8.50020-9 SP - 321 EP - 325 PB - Elsevier CY - Amsterdam ER - TY - GEN A1 - Hirsch, Thomas A1 - Shaporenko, Andrey A1 - Mirsky, Vladimir M. A1 - Zharnikov, Michael T1 - Monomolecular films of phthalocyanines: formation, characterisation and expelling by alkanethiols T2 - Langmuir N2 - Adsorption of aluminum-2,3-naphthalocyanine (Al-PC) onto gold (111) substrate from the pure and mixed (with alkanethiols) solutions of the target molecules in ethanol was studied. The resulting films were characterized by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. The adsorption from the pure solution resulted in formation of an Al-PC monolayer composed of the strongly inclined molecules. However, a presence of only one molar percent of a thiolated compound (alkanethiol) in the primary solution led to the complete expelling of the Al-PC molecules from the substrate and formation of a one-component alkylthiolate monolayer. The results indicate that an equilibrium formation of mixed monolayers of rodlike thiolated molecules and relatively large planar-geometry molecules, whose interaction with the metal surface is mainly provided by the π-electron system, is difficult to achieve or is in most cases even impossible under equilibrium conditions and requires an introduction of additional anchor moieties (e.g., thiols) into these molecules, as has been demonstrated by successful coadsorption of hexadecanethiol and thiolated tetraphenylporphyrin. Y1 - 2007 U6 - https://doi.org/10.1021/la0634239 SN - 0743-7463 SN - 1520-5827 VL - 23 IS - 8 SP - 4373 EP - 4377 ER - TY - GEN A1 - Cao, Limin A1 - Lin, Hong A1 - Mirsky, Vladimir M. T1 - DNA-based surface plasmon resonance biosensor for enrofloxacin T2 - Analytica Chimica Acta N2 - A DNA-based surface plasmon resonance biosensor for enrofloxacin was developed. Heating denatured DNA immobilized on the gold-coated glass surface was exploited. The immobilization was performed by a layer-by-layer co-deposition with a cationic polymer. The sensor performance was tested with real biological probes. Direct and simple determination of enrofloxacin in milk samples was demonstrated. The sensor response obeys Langmuir binding isotherm being almost linear until about 20 µg per mL. The detection limit in milk samples was estimated to be 3 µg per mL. KW - Surface plasmon resonance KW - Nucleic acid KW - Biosensor KW - Enrofloxacin KW - Fluoroquinolones KW - Layer-by-layer deposition Y1 - 2007 U6 - https://doi.org/10.1016/j.aca.2007.02.034 SN - 0003-2670 VL - 589 IS - 1 SP - 1 EP - 5 ER - TY - GEN A1 - Cao, Limin A1 - Lin, Hong A1 - Mirsky, Vladimir M. T1 - Detection of antibiotics in food: Extraction of fluoroquinolones by DNA T2 - Analytical and Bioanalytical Chemistry N2 - The ability of DNA to extract fluoroquinolones from model solutions and real probes of food was demonstrated and investigated quantitatively. The interaction between fluoroquinolones and different types of DNA was studied by equilibrium dialysis. The first application of this direct approach allowed us to determine binding constants and binding stoichiometries in different conditions. The binding of enrofloxacin to heat-denatured DNA (d-DNA) from herring sperm is pH- and magnesium-dependent; the highest fraction of bound drugs was found at pH 7 and a magnesium concentration of 0.5–1 mM. Results for three types of DNA: d-DNA, double-stranded DNA and single-stranded DNA were compared. The unwound DNA showed almost doubled binding constants and stoichiometries, thus indicating preferable interaction of enrofloxacin with single-strand regions of DNA. The binding of other fluoroquinolones (lomefloxacin, ciprofloxacin, norfloxacin, danofloxacin and sarafloxacin) with d-DNA is very similar to that of enrofloxacin: the binding constants are in the range from 0.94 × 105 to 2.40 × 105 M−1, and the stoichiometries range from 4.1 to 6.9 fluoroquinolone molecules per 100 DNA bases. The binding properties were quantitatively the same for extraction of fluoroquinolones from model aqueous solutions and from liquid food (milk). The results indicate the efficiency of DNA for selective extraction of fluoroquinolones from real samples for further analysis. This selective binding also allows us to consider DNA as a natural receptor for development of analytical techniques for fluoroquinolones. KW - Fluoroquinolone KW - DNAExtraction KW - Binding constant KW - Binding stoichiometry Y1 - 2007 U6 - https://doi.org/10.1007/s00216-007-1191-5 SN - 1618-2642 SN - 1618-2650 VL - 388 IS - 1 SP - 253 EP - 258 ER - TY - CHAP A1 - Vasjari, Majlinda A1 - Mirsky, Vladimir M. ED - Alegret, Salvador ED - Merkoci, Arben T1 - Chemoresistor for determination of mercury vapor T2 - Electrochemical Sensor Analysis N2 - This chapter presents a procedure to prepare and calibrate chemical sensor for mercury vapor and discusses application of the sensor for measurements of mercury vapor. The sensor is based on high affinity of gold to mercury and on chemoresistive properties of ultrathin gold layers: adsorption of mercury leads to increase in the surface resistance. However, this effect is not selective: similar changes are caused by adsorption of water vapor and sulfuric compounds. The use of monomolecular layer of alkylthiols as a filter excludes this interference completely. Sensor calibration is performed by thermoinjection of nanogram-amount of mercury quantitatively deposited by electrochemical reduction. It is found that the sensors display no sensitivity to such typical interferents of mercury chemoresistors based on uncoated gold as volatile thiols and water. Preliminary data demonstrate a possibility to measure Hg(0) even in aqueous solutions. Y1 - 2007 SN - 978-0-444-53053-0 U6 - https://doi.org/10.1016/S0166-526X(06)49058-9 SP - 105 EP - 109 PB - Elsevier CY - Amsterdam ER - TY - CHAP A1 - Mirsky, Vladimir M. A1 - Vasjari, Majlinda ED - Alegret, Salvador ED - Merkoci, Arben T1 - Chemical sensors for mercury vapour T2 - Electrochemical Sensor Analysis N2 - A number of analytical methods were developed for determination of elemental mercury. They include traditional analytical techniques, such as atomic adsorption spectroscopy (AAS), atomic fluorescence spectroscopy (AFS), and atomic emission spectroscopy (AES). Other analytical methods include neutron-activation analysis and laser photo-acoustic spectroscopy (detection limit about 5 μg/l). To increase sensitivity and selectivity of these methods, a preconcentration of mercury is widely performed. This can be realized by exploring high affinity of mercury to gold. Mercury and its volatile compounds can easily be adsorbed on gold at normal temperatures and can be released quantitatively upon heating. Hence, gold has been used as an adsorbent for the accumulation of mercury to a concentration sufficient for further spectroscopic analyses. The main disadvantage of mercury sensors based on bare gold layers is their poor selectivity and applications of such sensors for real probes and makes necessary a pre-treatment of probes. Mercury sensors based on thin gold layers require regular calibrations. In ideal cases, the calibration should be performed before each measurement. Therefore, a calibration technique should be compatible with design and concept of the mercury vapor sensor. Y1 - 2007 SN - 978-0-444-53053-0 U6 - https://doi.org/10.1016/S0166-526X(06)49012-7 SP - 235 EP - 251 PB - Elsevier CY - Amsterdam ER - TY - GEN A1 - Roznyatovskaya, Nataliya V. A1 - Laurinavichyute, Veronika K. A1 - Tsirlina, Galina A. A1 - Mirsky, Vladimir M. T1 - Electrochemistry and catalytic behavior of immobilized binuclear complexes of copper(II) and nickel(II) with Robson type ligand T2 - Journal of Solid State Electrochemistry N2 - Various systems containing immobilized binuclear copper(II) and nickel(II) complexes with Robson type ligand ([M2L]Cl2) are studied and compared in relation to catalysis of hydrogen peroxide reduction. Molecular complexes adsorbed on mercury and gold, crystalline complexes immobilized in the carbon paste electrode, and complex species entrapped into polyphenol-modified gold electrodes are considered. Electrocatalysis is assumed to result from the formation of H2O2–[M2L]Cl2 adduct, not from mediating redox transformations. Possible geometry of the formed reaction layers supporting adduct formation is discussed. KW - Binuclear copper macrocyclic complex KW - Cyclic voltammetry KW - Adsorption KW - Carbon paste electrodes KW - Electroreduction Y1 - 2007 U6 - https://doi.org/10.1007/s10008-006-0235-7 SN - 1432-8488 SN - 1433-0768 VL - 11 IS - 7 SP - 981 EP - 992 ER - TY - GEN A1 - Hao, Qingli A1 - Wang, Xin A1 - Lu, Lude A1 - Yang, Xujie A1 - Mirsky, Vladimir M. T1 - Electropolymerized multilayer conducting polymers with response to gaseous hydrogen chloride T2 - Macromolecular Rapid Communications N2 - A step-by-step ‘all-electrochemical’ approach has been presented to develop a multilayer structure of conducting polymers for gas sensors. The integrated structure includes a sensitive layer (polyaniline, PANI) and a conductive bridge consisting of poly(3,4-ethylenedioxythiophene) (PEDOT). Good sensitivity, stability, and response of the multilayer material to gaseous HCl indicate a possible application of conductive polymers to provide a binding of sensitive elements in sensors or other fields. The conducting multilayer material, Au/pATP/PANI/PEDOT, was synthesized electrochemically. Y1 - 2005 U6 - https://doi.org/10.1002/marc.200500114 SN - 1521-3927 VL - 26 IS - 13 SP - 1099 EP - 1103 ER - TY - GEN A1 - Mirsky, Vladimir M. A1 - Kulikov, Valentin A1 - Wolfbeis, Otto S. T1 - Complete system for combinatorial synthesis and functional investigation of conductive polymers T2 - American Chemical Society PMSE Preprints N2 - Complete system for combinatorial electrochemical synthesis and functional characterization of combinatorial libraries formed by different polymers and polymeric structures will be presented. Control of electrical potential of single electrode groups consisting of four electrodes (designed for 4-point measurements ) on the array comprising 96 such electrode groups provides addressable electrochemical polymer synthesis on the defined electrodes. After polymerization, electrical characteristics of polymers or/and polymer/electrode contacts and influence of potential analytes on these characteristic are measured. Final data analysis provides complete analytically relevant information on the investigated thin polymer layers or multilayer polymer structures: absolute and relative sensitivity, response time, reversibility, reproducibility, regeneration kinetics, linearity or binding constant. Examples of applications for the development of gas-sensitive (co)polymers and optimization of their sensitive properties and polymer/metal contacts will be presented. Y1 - 2005 VL - 93 SP - 1053 ER - TY - GEN A1 - Hirsch, Thomas A1 - Zharnikov, Michael A1 - Shaporenko, Andrey A1 - Stahl, Joachim A1 - Weiss, Dieter A1 - Wolfbeis, Otto S. A1 - Mirsky, Vladimir M. T1 - Size-controlled electrochemical synthesis of metallic nanoparticles on molecular templates T2 - Angewandte Chemie International Edition N2 - Reduction on the spot: Planarly adsorbed thiolated porphyrin molecules (purple) incorporated in an insulating alkanethiol monolayer (blue) function as nanoelectrodes for the local reduction of metals (gray). This approach was applied for the in situ synthesis of nanoparticles of a predetermined size. Y1 - 2005 U6 - https://doi.org/10.1002/anie.200500912 SN - 1521-3773 VL - 44 IS - 41 SP - 6775 EP - 6778 ER - TY - GEN A1 - Zybin, Alexander A1 - Grunwald, Christian A1 - Mirsky, Vladimir M. A1 - Kuhlmann, Jürgen A1 - Wolfbeis, Otto S. A1 - Niemax, Kay T1 - Double-wavelength technique for surface plasmon resonance measurements: basic concept and applications for single sensors and two-dimensional sensor arrays T2 - Analytical Chemistry N2 - A new technique for on-line monitoring of analyte binding to sensor surfaces by surface plasmon resonance (SPR) detection is described. It is based on differential measurements using two wavelengths provided by two diode lasers. The technique is as simple and robust as the conventional SPR detection measuring the reflected radiation at fixed incidence angle, but it has the advantage of being nonsensitive to variations of the resonance width and providing essentially higher signal/noise ratios. The paper presents the first four channel prototype system for parallel 2D-monitoring at four different spots. One channel is always used as a reference to compensate temperature fluctuations and nonspecific adsorptions. Calibration with sucrose solutions revealed an absolute sensitivity of Δn ∼ 5 × 10-6. The new technique is tested with a biotin−streptavidin binding and with hybridization/denaturation of DNA. Biotin binding to a streptavidin monolayer is detected with a signal/noise ratio of about 5, which demonstrates the high potential of the new technique for applications in drug discovery. Applications to gene analysis are tested with short oligonucleotides of the sequences used for genotyping human hepatitis C viruses. A selective response to complementary oligonucleotides is observed. The high reproducibility in subsequent cycles of hybridization/denaturation (by formamide or by heating) points out potential applications of the technique in medical diagnostics, food industry, genomics, and proteomics too. Y1 - 2005 U6 - https://doi.org/10.1021/ac048156v SN - 0003-2700 SN - 1520-6882 VL - 77 IS - 8 SP - 2393 EP - 2399 ER - TY - CHAP A1 - Mirsky, Vladimir M. A1 - Kulikov, Valentin A1 - Hao, Qingli A1 - Wolfbeis, Otto S. T1 - Application of combinatorial electropolymerization to the development of chemical Sensors T2 - Combinatorial and artificial intelligence methods in materials science II, symposium held December 1 - 4, 2003, Boston, Massachusetts, U.S.A. N2 - Combinatorial electropolymerization with electrical addressing was realized on the array of 96 electrode groups, each from four electrodes. The polymer synthesis was combined with subsequent high-throughput investigation of analytical properties of synthesized polymers. Two-and four-point techniques were applied simultaneously to measure electrical properties of synthesized polymers and contact resistances between electrodes and polymers and modifications of these parameters on addition of analyte. The system was used for development of sensitive materials for detection of gaseous hydrogen chloride. Y1 - 2004 SN - 1-55899-742-3 U6 - https://doi.org/10.1557/PROC-804-JJ4.1 SP - 111 EP - 116 PB - Materials Research Society CY - Warrendale, Pa. ER - TY - GEN A1 - Samoylov, Anton V. A1 - Mirsky, Vladimir M. A1 - Hao, Qingli A1 - Swart, Claudia A1 - Shirshov, Yuri M. A1 - Wolfbeis, Otto S. T1 - Nanometer-thick SPR sensor for gaseous HCl T2 - Sensors and Actuators B: Chemical N2 - The optical properties of electrochemically polymerized N-methylaniline are changed in the presence of gaseous hydrogen chloride. This effect was used for preparation of chemical sensors with transduction based on surface plasmon resonance. The interaction of hydrogen chloride with a two nm layer of poly-(N-methylaniline) on gold leads to the shift of the surface plasmon resonance. The analysis of the resonance spectra demonstrates that the effect is caused by an increase of the imaginary component of the refractive index; a minor contribution is also provided by film condensation leading to an increase of the real component of the refractive index and a decrease in the thickness. The effect is selective and quasi-reversible. The concentration dependence of the gas effect obeys Langmuir's adsorption isotherm with a reciprocal value of the binding constant of 850 ± 160 ppm. KW - Gas sensor KW - HCI sensors KW - Surface plasmon resonance KW - Electropolymerization KW - Poly-(N-methyl-aniline) KW - Fire detector Y1 - 2005 U6 - https://doi.org/10.1016/j.snb.2004.08.029 SN - 0925-4005 VL - 106 IS - 1 SP - 369 EP - 372 ER - TY - GEN A1 - Kurniawan, Fredy A1 - Tsakova, Vessela T. A1 - Mirsky, Vladimir M. T1 - Gold nanoparticles in non-enzymatic electrochemical detection of sugars T2 - Electroanalysis N2 - A nonenzymatic electrochemical sensor for detection of sugars was prepared by layer-by-layer deposition of gold nanoparticles on thin gold electrodes. The deposition was optimized by using of surface plasmon resonance. Voltammetric investigation and impedance spectroscopy of the sensor was performed. Electrical currents caused by glucose on bare gold electrodes and on gold electrodes coated by immobilized gold nanoparticles were compared. The electrodes with nanoparticles display much higher current of glucose oxidation. The oxidation becomes blocked when the swept electrode potential exceeded +0.25 V, during the back scan an oxidation peak is observed again but at less positive potential. The magnitudes of these current peaks are linearly dependent on the glucose concentration; this dependence can be used as calibration for analytical applications. The limit of detection for glucose is below 0.5 mM, the sensitivity (normalized to the macroscopic electrode surface) is about 160 μA cm-2 mM-1. The sensor response is linear till at least 8 mM of glucose concentration. KW - Gold nanoparticles KW - Electrochemical KW - Glucose detection Y1 - 2006 U6 - https://doi.org/10.1002/elan.200603607 SN - 1521-4109 VL - 18 IS - 19-20 SP - 1937 EP - 1942 ER - TY - GEN A1 - Mirsky, Vladimir M. T1 - Neue Technologie angewandter Polymerforschung. Hundert mal schneller zu neuen Sensormaterialien T2 - Aktuelle Wochenschau : HighChem hautnah. Aktuelles aus der analytischen Chemie Y1 - 2005 VL - 48 SP - 98 EP - 99 ER - TY - GEN A1 - Ivanov, Svetlozar D. A1 - Tsakova, Vessela T. A1 - Mirsky, Vladimir M. T1 - Conductometric transducing in electrocatalytical sensors: Detection of ascorbic acid T2 - Electrochemistry Communications N2 - Conductometric transducing is suggested for electrocatalytic chemical sensors based on conductive polymers. Lateral conductivity of the polymer layers was measured by two- and four-point techniques. The approach was applied for electroanalytical detection of ascorbic acid on the electrocatalytically active polyaniline and poly-ortho-methoxyaniline electrodes. Both polymers displayed a monotonous concentration dependence of their conductance in the analytically important sub-millimolar concentration range of ascorbic acid. The approach was tested in model solutions of ascorbic acid in buffer and applied for detection of ascorbic acid in orange juice. KW - Chemical sensor KW - Conductometric sensor KW - Ascorbic acid KW - Electrocatalytical sensor KW - Electroactive polymers KW - Polyaniline KW - Poly-ortho-methoxyaniline Y1 - 2006 U6 - https://doi.org/10.1016/j.elecom.2006.02.006 SN - 1388-2481 VL - 8 IS - 4 SP - 643 EP - 646 ER - TY - GEN A1 - Zhi, Zheng-liang A1 - Drazan, Viktor A1 - Wolfbeis, Otto S. A1 - Mirsky, Vladimir M. T1 - Electrocatalytic activity of DNA on electrodes as an indication of hybridization T2 - Bioelectrochemistry N2 - Electron transfer between metal electrodes and ferro/ferricyanide is completely suppressed at low ionic concentration. We describe here a new phenomenon related to this reaction: an immobilisation of thiolated single-stranded DNA on gold electrodes retains this activity at low ionic strength up to the level corresponding to the high ionic strength. In contrast, a hybridisation of the complementary DNAwith the thiolated single-stranded DNA followed by a binding onto the electrodes, attenuated the electrocatalytic effect. These effects can be used for discrimination between single-stranded DNA and double-stranded DNA and for semi-quantitative measurement of complementary DNA in a sample. KW - DNA KW - DNA-sensor KW - Biosensor KW - Electrocatalysi KW - Hybridisation KW - Oligonucleotide KW - Gene analysis Y1 - 2006 U6 - https://doi.org/10.1016/j.bioelechem.2005.02.006 SN - 1567-5394 VL - 68 IS - 1 SP - 1 EP - 6 ER - TY - GEN A1 - Krondak, Martin A1 - Broncová, Gabriela A1 - Anikin, Sergey A1 - Merz, Andreas A1 - Mirsky, Vladimir M. T1 - Chemosensitive properties of poly-4,4'-dialkoxy2,2’-bipyrroles T2 - Journal of Solid State Electrochemistry N2 - Chemosensitive properties of 4,4′-dimethoxy-2,2′-bipyrrole and 4,4′-dibuthoxy-2,2′-bipyrrole were investigated. These new conductive polymers were polymerized by cyclic voltammetry on the platinum and gold interdigitated electrodes designed for 2- and 4-point measurement of lateral conductivity. Thus, obtained polymers demonstrated high sensitivity to HCl in the parts per million concentration range. Kinetics of the gaseous HCl influence on the ratios of conductivities measured by 2- and 4-point techniques was analyzed. Some response of the polymers conductance towards NH3, NO and oxygen was also observed, but with much lower sensitivity than towards HCl. In aqueous solutions, the polymer conductivity was pH dependent; in comparison with 4,4′-dibuthoxy-2,2′-bipyrrole, the conductivity range of the methoxy derivative was shifted to acidic range for about two pH units. A possibility to use the pH dependence for the development of enzymatic biosensors with pH transducing was demonstrated. KW - Conductive polymer KW - Sensor KW - Conductivity KW - HCI KW - Alkoxybipyrroles Y1 - 2006 U6 - https://doi.org/10.1007/s10008-005-0069-8 SN - 1432-8488 SN - 1433-0768 VL - 10 IS - 3 SP - 185 EP - 191 ER - TY - GEN A1 - Mirsky, Vladimir M. A1 - Kulikov, Valentin A1 - Hao, Qingli A1 - Wolfbeis, Otto S. T1 - Multiparameter High Throughput Characterization of Combinatorial Chemical Microarrays of Chemosensitive Polymers T2 - Macromolecular Rapid Communications N2 - High throughput characterization of combinatorial libraries demands a compromise between completeness of the study and reasonable investigation time. This compromise can be found by the development of test protocols consisting of the minimal number of the most informative measurements. Multiparameter high throughput characterization of sensitive materials is described. The parameters include response time, regeneration time, reversibility, reproducibility, sensitivity, linearity. The approach was applied for characterization of conductometric gas-sensitive polymer materials. Chemical microarrays prepared by electrochemical synthesis of polymers on platinum electrodes. Y1 - 2004 U6 - https://doi.org/10.1002/marc.200300210 SN - 1521-3927 VL - 25 IS - 1 SP - 253 EP - 258 ER -