Synthesizing of a nanocomposite based on the formation of silver nanoparticles on fumed silica to develop an electrochemical sensor for carbendazim detection.

In this study, a nanocomposite was synthesized via the formation of silver nanoparticles on fumed silica (FS@Ag) to prepare an electrochemical sensor for the determination of carbendazim (CBZ), a common pesticide. The electrochemical sensor was designed by the combination of the carbon paste electrode (CPE) with the FS@Ag nanocomposite. Based on the electrochemical sensor prepared here, a voltammetric method was developed for the determination of CBZ in water and food samples. Characterization of the nanocomposite was conducted by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray analyses. Modified electrodes were also electrochemically characterized via cyclic voltammetry and electrochemical impedance spectroscopy analyses. The FS@Ag showed electrocatalytic activity on the electrochemical oxidation of CBZ via increasing the peak currents tremendously. With the proposed method, a very low limit of detection (9.4 × 10-10 M) and a wide linear range (5.0 × 10-8 M - 3.0 × 10-6 M) were obtained for CBZ. The slope of the calibration line obtained with CPE/15FS@Ag was 194-times higher than that of bare CPE, indicating the high sensitivity of the electrochemical sensor. The performance of the electrochemical sensor has been investigated in real samples such as river water, tomato juice, orange juice, and apple juice samples. The results reveal that the electrochemical sensor prepared here can be used as an alternative to current analytical methods used for the quantification of CBZ.

Preparation of a disposable and low-cost electrochemical sensor for propham detection based on over-oxidized poly(thiophene) modified pencil graphite electrode.

In this study, an electrochemical sensor was developed for the determination of propham (PRO) in potato, human urine and river water samples based on the over-oxidized poly(thiophene) modified pencil graphite [PG/p(Thp)-Ox] electrode. Adsorptive stripping differential pulse voltammetry was used as a voltammetric method. The PG/p(Thp)-Ox electrode increased the oxidation peak current of PRO 30 times according to bare PG. Electrochemical polymerization and over-oxidation conditions were deeply optimized to increase the sensitivity of PG/p(Thp)-Ox. Characterization of PG/p(Thp)-Ox was performed via scanning electron microscopy and cyclic voltammetry analysis. Oxidation peak current value of PRO linearly increased with the concentration of PRO in the ranges of 0.005-1.0 µM and 2.0-15.0 µM. A very low limit of detection value (1.0 nM) was obtained. Intra-day and inter-day reproducibility of the PG/p(Thp)-Ox were determined as 2.96% (N: 10) and 4.77% (10 days), respectively. Satisfactory recovery values (98.07-104.4%) were observed with PG/p(Thp)-Ox electrode during the analysis of PRO in PRO-spiked potato, urine and river water samples. The results show that the PG/p(Thp)-Ox could be used safely in the determination of PRO.

Investigation of applicability of Electro-Fenton method for the mineralization of naphthol blue black in water.

In this study, mineralization and color removal performance of electro-Fenton method were examined in water containing naphthol blue black (NBB), a diazo dye. NBB was totally converted to intermediate species in a 15-min electrolysis at 60 mA, but complete de-colorization took 180 min. A very high oxidation rate constant ((3.35 ±â€¯0.21) x 1010 M-1s-1) was obtained for NBB, showing its high reactivity towards hydroxyl radicals. A very high total organic carbon (TOC) removal value (45.23 mg L-1) was obtained in the first 60 min of the electro-Fenton treatment of an aqueous solution of NBB (0.25 mM) at 300 mA, indicating the mineralization efficiency of the electro-Fenton method. Mineralization current efficiency values obtained at 300 mA gradually decreased from 24.18% to 4.47% with the electrolysis time, indicating the presence of highly parasitic reactions. Gas chromatography-mass spectrometry analyses revealed that the cleavage of azo bonds of NBB led to formation of different aromatic and aliphatic oxidation intermediates. Ion chromatography analysis showed that ammonium, nitrate and sulfate were the mineralization end-products. The concentration of sulfate ion reached to its quantitative value at the 4th h of electrolysis. On the other hand, the total concentration of ammonium and nitrate ions reached to only 61% of the stoichiometric amount of initial nitrogen after a 7 h electrolysis. Finally, it can be said that the electro-Fenton method is a suitable and efficient method for the removal of NBB and its intermediates from water.

Bioconjugated and cross-linked bionanostructures for bifunctional immunohistochemical labeling.

The present study describes the development and use of a new bioconjugate combining targeted quantum dot labeling with an immunoperoxidase method and explores whether these bioconjugates could specifically and effectively label Cu/Zn superoxide dismutase (SOD1). The new bioconjugate is designed for the examination of samples both under fluorescent and bright-field microscopy at the same time. For this purpose chlorobis(2-2'-bipyridyl) methacryloyl tyrosine-ruthenium(II) and bis (2-2'-bipyridyl) methacryloyltyrosine-methacryloyltryptophan-ruthenium (II) photosensitive monomers and photosensitive poly(Bis (2-2'-bipyridyl)) methacryloyltyrosine-methacryloyltryptophan-ruthenium(II) were synthesized and characterized. The anti-SOD1 antibody and horseradish peroxidase (HRD) conjugated quantum dots were prepared by using this polymer. The anti-SOD1 antibody and HRD conjugated quantum dots were used in labeling and imaging of SOD1 in rat liver sections. Quantum dot particles were observed as a bright fluorescence in their specific binding locations inside the hepatocytes. The HRD-diaminobenzidine reaction product was observed as brown-colored particles at the same locations under bright-field microscopy. Structural details of the tissue sections could be examined at the same time. The conjugation protocol is simple; the bioconjugate is applicable for efficient cell labeling and can be adapted for imaging of other targets in different tissues. Also, the prepared nanobioconjugates have mechanic stability and can be used for a long period.

Investigation of photosensitively bioconjugated targeted quantum dots for the labeling of Cu/Zn superoxide dismutase in fixed cells and tissue sections.

This study presents the development of targeted and antibody cross-linked QDs and explores whether these bioconjugates could specifically and effectively label Cu/Zn superoxide dismutase (SOD1) on fixed cells and tissues. QD-antibody conjugation was achieved by using our previously invented AmiNoacid (monomer) Decorated and Light Underpining Conjugation Approach (ANADOLUCA) method. In this method, we have used a photosensitive aminoacid monomer having ruthenium complex which is a synthetic and inexpensive material for the preparation of bioconjugates. Its specificity was demonstrated by extracting the active enzyme from rat liver lysate by using the bioconjugate. It provided accurate antibody orientation, high specificity and mechanic stability. The protocol steps for QD-antibody conjugation and specimen preparation were described in detail. The nanobioconjugates were prepared under mild conditions (for example in day light), independent of pH and temperature, without affecting conformation and function of protein. This protocol is simple, inexpensive and can be successfully adapted to detect other targets on different cell types and tissues.

Preparation of new molecularly imprinted quartz crystal microbalance hybride sensor system for 8-hydroxy-2'-deoxyguanosine determination.

The routine measurement of 8-hydroxy-2'-deoxyguanosine (8-OHdG) in biological samples is a difficult analytical problem due to the low levels of the analyte and complex matrix. A new 8-OHdG imprinted quartz crystal microbalance (QCM) sensor has been developed for selective determination of 8-OHdG in serum samples. To fulfil the desired results, we have used methacryloyl aminoantipyrine-Fe(III) [MAAP-Fe(III)] and methacryloyl histidine-Pt(II) [MAH-Pt(II)] as metal-chelating monomers via double metal coordination-chelation interactions for the preparation of additional selective molecular imprinted polymers (MIP). The study includes the measurement of binding interaction of 8-OHdG imprinted quartz crystal microbalance (QCM) sensor, selectivity experiments and analytical performance of QCM chip. The obtained results have showed that the application of double metal-chelate monomer systems has been more effective than single metal-chelate monomer systems. In this study, the detection limit and the linear working range were found to be 0.0075 and 0.0100-3.5 microM, respectively. The affinity constant (K(affinity)) was found to be 1.54x10(5) M(-1) for 8-OHdG using MAH-Pt-8-OHdG-MAAP-Fe based thin film. Also, selectivity of prepared QCM sensor was found as being very high in the presence of competitive species. At the last step of this procedure, 8-OHdG level in blood serum which belongs to a intestinal cancer patient was determined by the prepared QCM sensor.

L-histidine imprinted synthetic receptor for biochromatography applications.

We have proposed novel surface-imprinted beads for selective separation of cytochrome c (cyt c) by N-methacryloyl-(L)-histidine-copper(II) [MAH-Cu(II)] as a new metal-chelating monomer via metal coordination interactions and histidine template. We have combined molecular imprinting with the ability of histidine to chelate metal ions to create ligand exchange beads suitable for the binding of cyt c (surface histidine exposed protein). The histidine imprinted beads were produced by suspension polymerization of MAH-Cu(II)-L-histidine and ethylene glycol dimethacrylate. After polymerization, the template (L-histidine) was removed from the beads using methanolic KOH, thus getting histidine imprinted metal-chelate beads. L-Histidine imprinted metal-chelate beads can be used several times without considerable loss of cyt c adsorption capacity. The association constant (Ka) for the specific interaction between the template imprinted polymer and the template (L-histidine) itself were determined by Scatchard plots using L-histidine imprinted beads and found as 58,300 M(-1). Finally, we have used these histidine imprinted beads for cyt c and ribonuclease A (surface histidine exposed proteins) and enantiometric separation of D- and L-histidine by FPLC.