Electrografting of thionine diazonium cation onto the graphene edges and decorating with Au nano-dendrites or glucose oxidase: Characterization and electrocatalytic applications.

Thionine (Th) diazonium cation is covalently attached onto the glassy carbon (GC) electrode via graphene nanosheets (GNs) (GC-GNs-Th). The GC-GNs-Th electrode is subjected to further modifications to fabricate (i) glucose and (ii) nitrite sensors. Further modifications include: (i) direct immobilization of glucose oxidase (GOx) and (ii) electrodeposition of gold dendrite-like nanostructures (DGNs) on the GC-GNs-Th surface, constructing GC-GNs-Th-GOx and GC-GNs-Th-DGNs modified electrodes, respectively. The GC-GNs-Th-GOx biosensor exhibited a linear response range to glucose, from 0.5 to 6.0mM, with a limit of detection (LOD) of 9.6 µM and high sensitivity of 43.2 µAcm(-2)mM(-1). Also, the GC-GNs-Th-DGNs sensor showed a wide dynamic response range for NO2(-) ion with two linear parts, from 0.05 µM to 1.0 µM and 30.0 µM to 1.0mM, a sensitivity of 263.2 µAmM(-1) and a LOD of 0.01 µM. Applicability of the modified electrodes was successfully tested by determination of glucose in human blood serum and nitrite in water based on addition/recovery tests.

Characterization of gold-thiol-8-hydroxyquinoline self-assembled monolayers for selective recognition of aluminum ion using voltammetry and electrochemical impedance spectroscopy.

Gold electrode surface is modified via covalent attachment of a synthesized thiol functionalized with 8-hydroxyquinoline, p-((8-hydroxyquinoline)azo) benzenethiol (SHQ), for the first time. The behavior of the nanostructured electrode surface (Au-SHQ) is characterized by electrochemical techniques including cyclic and differential pulse voltammetry (CV and DPV), and electrochemical impedance spectroscopy (EIS). The modified surface is stable in a wide range of potentials and pHs. A surface pKa of 6.0±0.1 is obtained for Au-SHQ electrode using surface acid/base titration curves constructed by CV and EIS measurements as a function of pH. These results helped to determine the charge state of the surface as a function of pH. The gold modified electrode surface showed good affinity for sensing the Al(III) ion at pH 5.5. The sensing process is based on (i) accumulation and complex formation between Al(III) from the solution phase and 8HQ function on the Au electrode surface (recognition step) and (ii) monitoring the impedance of the Au-SHQ-Al(III) complex against redox reaction rate of parabenzoquinone (PBQ) (signal transduction step). The PBQ is found to be a more suitable probe for this purpose, after testing several others. Thus, the sensor was tested for quantitative determination of Al(III) from the solution phase. At the optimized conditions, a linear response, from 1.0×10(-11) to 1.2×10(-5) M Al(III) in semi-logarithmic scale, with a detection limit of 8.32×10(-12) M and mean relative standard deviation of 3.2% for n=3 at 1.0×10(-7) M Al(III) is obtained. Possible interferences from coexisting cations and anions are also studied. The results show that many ions do not interfere significantly with the sensor response for Al(III). Validity of the method and applicability of the sensor are successfully tested by determination of Al(III) in human blood serum samples.

Direct electrochemistry of cytochrome c immobilized on gold electrode surface via Zr(IV) ion glue and its activity for ascorbic acid.

Direct electrochemistry of cytochrome c (Cyt c) is achieved via Zr(IV) ion as an immobilization matrix to interface Cyt c on gold surface via thiol self-assembled monolayers. Steps of surface modification and electrocatalytic activity of the immobilized Cyt c are followed by voltammetry, impedance spectroscopy, chronoampetrometry, and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The results indicate that the native structure of Cyt c is conserved during the immobilization process. The immobilization method is rather simple, effective and free of immobilizing activators and reagents. Direct electron transfer rate constant and surface coverage of the immobilized Cyt c are found as 8.62(±1.98) s(-1) and 1.15(±0.38)×10(-11)molcm(-2), respectively. Bioactivity studies of the immobilized Cyt c toward oxidation of the ascorbic acid (AA) substrate show a linear response, from 10.0µM to 1.30mM AA, with a detection limit of 5.0(±1.8) µM AA and mean relative standard deviations varied from 13.7% to 3.7% for n=4 at each point. A value of 1.6(±0.8) mM AA is found for the Michaelis-Menten constant of Au-MPA-Zr(IV)-Cyt c toward AA for the first time. The tightly immobilized Cyt c maintains its bioactivity for more than 32days storage at 4°C.

Electrochemical monitoring of the interaction of UO2(2+) with immobilized DNA.

Interaction of uranyl ion (UO2(2+)) with immobilized double strand calf thymus DNA (ds-ct-DNA) on zirconium attached gold-mercaptopropionic acid self-assembled monolayer (Au-MPA-Zr(IV) SAM) is monitored by electrochemical techniques. The results show that after 15 min proximity of the immobilized DNA with UO2(2+), the peak currents of the square wave voltammograms are decreased (about 80%), and the equivalent circuit model of electrochemical impedance spectroscopy (EIS) data, requires two constant phase elements (CPE) instead of only one. By using the surface concentration of DNA (≈2.3×10(-13) mol/cm(2)) and the number of the anthraquinonedisulfonic acid (AQDS) adsorbed on DNA (1.34×10(-10) mol/cm(2)) the ration of AQDS per DNA base pairs is obtained ≈1/30 before proximity to UO2(2+). Based on EIS technique, we find that the double strand structure of immobilized DNA on the electrode surface has been changed (damaged) by UO2(2+). This modified electrode has potential of becoming a screening tool for the rapid assessment of the interaction and genotoxicity of existing and new chemicals.

Gold-deferrioxamine nanometric interface for selective recognition of Fe(III) using square wave voltammetry and electrochemical impedance spectroscopy methods.

Deferrioxamine, a bacterial hydroxamic siderophore having high binding affinity for Fe(III), is used in its immobilized form, as self-assembled monolayer on Au, for accumulation and recognition of Fe(III) from the solution phase. The accumulated Fe(III) is detected via both active mode based on faradaic reduction current of Fe(III), and inactive mode based on impedimetric effect of accumulated Fe(III) against redox reaction of a suitable probe. Appropriate electrochemical techniques, square wave voltammetry and electrochemical impedance spectroscopy, are used for the transduction of analytical signals obtained by this sensor. Then, the parameters influencing the sensor response are optimized. In the best conditions, a linear response, from 1.0×10(-10) to 1.0×10(-7)M Fe(III) in logarithmic scale with a detection limit of 2.0×10(-11)M, and mean relative standard deviation of 1.7% for n=4 is observed. The results show that the sensor can be used for determination of Fe(III) in the presence of various inorganic ions and biological species. Validity of the method and applicability of the sensor are successfully tested by determination of Fe(III) in various real samples including plant tissue (corn leaves), industrial alloy (Ferrotitanium), and pharmaceutical samples (Venofer(®) ampoule, Ironorm(®) capsule, and V.M. Protein(®) powder).

Direct electrochemistry of dopamine on gold-Agaricus bisporus laccase enzyme electrode: characterization and quantitative detection.

Direct electrochemistry of a new laccase enzyme immobilized on gold and its application as a biosensor for dopamine (DA) are investigated by voltammetry and electrochemical impedance spectroscopy. The sensor demonstrated a redox adsorption behavior with E(0') = + 180 mV vs. Ag/AgCl for immobilized Agaricus bisporus laccase (LacAB) enzyme. The MPA platform was assembled on Au with and without utilization of ultrasounds. Excellent results were obtained by using the enzyme electrode fabricated based on MPA assembled with sonication. The LacAB immobilized in this condition showed a large electrocatalytic activity for oxidation of DA. Accordingly, a third-generation (mediator free) biosensor was constructed for DA. The DA concentration could be measured in the linear range of 0.5 to 13.0 and 47.0 to 430.0 µmol L(-1) with correlation coefficients of 0.999 and 0.989, respectively, and a detection limit of 29.0 nmol L(-1). The biosensor was successfully tested for determination of DA in human blood plasma and pharmaceutical samples.

Electrochemical determination of calf thymus DNA on Zr(IV) immobilized on gold-mercaptopropionic-acid self-assembled monolayer.

An electrochemical biosensor, constructed by immobilization of Zr(IV) on the topside of gold-mercaptopropionic acid self-assembled monolayer (Au-MPA-Zr SAM), is developed for the sensitive quantification of calf thymus DNA (ct-DNA). The sensor is based on ionic adsorption of ct-DNA from its phosphate backbone onto the Au-MPA-Zr(IV) SAM electrode. Preparation, characterization, and application of the sensor for determination of ct-DNA are described by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Osteryoung square wave voltammetry (OSWV) in the presence of an appropriate redox reaction probe. Parameters influencing the method have been tested. A linear range calibration curve from 1.0x10(-4) to 5.0x10(-7) g mL(-1) ct-DNA with a detection limit of 9.5x10(-8) g mL(-1) and mean of relative standard deviations (R.S.D) of 2.5% for n=4 at each point was observed in the best conditions by EIS. Regeneration of the surface was carried out successfully by 5 min sonication in 0.1 M KOH solution and then 1 min incubation in 1.0x10(-3) M Zr(IV) with a good reproducibility, R.S.D=1.5% for n=4 as detected by EIS. The long-term storage stability of the electrode was also studied.

Immobilization of L-lysine alpha-oxidase on gold-mercaptopropionic acid self-assembled monolayer: preparation and electrochemical characterization.

Immobilization of L-lysine alpha-oxidase on gold-mercaptopropionic acid self-assembled monolayer (Au-MPA-LOx SAM) electrode is verified experimentally in the present work. Fabrication steps and electrochemical interaction of Au-MPA-LOx with L-lysine were monitored by general electrochemical methods like cyclic voltammetry (CV) and chronoamperometry (CA), and by a more advanced method, electrochemical impedance spectroscopy (EIS) in the presence of parabenzoquinone (PBQ) redox probe. The data was analyzed from which quantitative kinetic parameters were extracted. The results confirmed successful immobilization of LOx, and thus, fabrication of Au-MPA-LOx SAM electrode. Our initial tests revealed a linear response for Au-MPA-LOx SAM electrode toward L-lysine concentration in solution at biological conditions, pH 7.4. The experimental data will be presented and discussed from which the Au-MPA-LOx SAM electrode is characterized, and the kinetic merits of the interface interactions are introduced.

Zirconium immobilized on gold-mercaptopropionic acid self-assembled monolayer for trace determination of phosphate in blood serum by using CV, EIS, and OSWV.

Preparation, characterization, and application of a new sensor for the determination of phosphate in blood serum is described by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and osteryoung square wave voltammetry (OSWV) in the presence of an appropriate redox reaction probe. The sensor was based on ionic adsorption of phosphate on Zr(IV) immobilized on gold-mercaptopropionic acid self-assembled monolayer (Au-MPA-Zr(IV) SAM) electrode. Parameters influencing the method were optimized. A linear range calibration curve from 1.0 x 10(-7) to 1.0 x 10(-6)M PO(4)(3-) with a detection limit of 5.30 x 10(-8)M and mean of relative standard deviations (R.S.D.) of 2.75% for n=4 was observed in the best conditions by OSWV. Possible interferences from the coexisting ions were also investigated. The results demonstrated that sensor could be used for the determination of phosphate in the presence of various ions. Regeneration of the surface was carried out successfully by 5-min sonication in 0.1M KOH solution and then 1-min incubation in 1.0x10(-3)M Zr(IV) with a good reproducibility, R.S.D.=1.47% for n=4 by OSWV. The validity of the method and applicability of the sensor were successfully tested by detection of phosphate in blood serum after deproteinization of sample without interference from sample matrix. The long-term storage stability of the electrode was studied. The experimental data is presented and discussed from which the new sensor is characterized.

Sensitive determination of iron(III) by gold electrode modified with 2-mercaptosuccinic acid self-assembled monolayer.

Preparation and application of gold 2-mercaptosuccinic acid self-assembled monolayer (Au-MSA SAM) electrode for determination of iron(III) in the presence of iron(II) is described by cyclic voltammetry, electrochemical impedance spectroscopy, and Osteryoung square wave voltammetry. The square wave voltammograms showed a sharp peak around positive potentials +0.250 V that was used for construction of the calibration curve. Parameters influencing the method were optimized. A linear range calibration curve from 1.0x10(-10) to 6.0x10(-9) M iron(III) with a detection limit of 3.0x10(-11) M and relative standard deviation (R.S.D.) of 6.5% for n=8 at 1.0x10(-9) M iron(III) was observed in the best conditions. Possible interferences from the coexisting ions were also investigated. The results demonstrated that sensor could be used for determination of iron(III) in the presence of various ions. The validity of the method and applicability of the sensor were successfully tested by determining of iron(III) in natural waters (tap and mineral waters) and in a pharmaceutical sample (Venofer ampoule) without interference from sample matrix. The experimental data are presented and discussed from which the new sensor is characterized.

Functionalization of gold cysteamine self-assembled monolayer with ethylenediaminetetraacetic acid as a novel nanosensor.

Electrochemical characterization of gold cysteamine self-assembled monolayer, in situ functionalized with ethylenediaminetetraacetic acid (Au-CA-EDTA SAM), is described by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Osteryoung square wave voltammetry (OSWV). The results obtained by EIS and CV, in the presence of [Fe(CN)(6)](3-/4-) redox probe, show that EDTA is successfully grafted to the surface of Au-CA electrode. Reproducible and reversible variation of the R(ct) and DeltaEp as a function of solution pH show that Au-CA-EDTA SAM is stable in a wide range of pH and potentials. Accumulation of the Pb(2+) and Cu(2+) ions on the Au-CA-EDTA SAM electrode is investigated using faradaic currents or impedimetric effects measured by OSWV and EIS, respectively. These results reveal the presence of active complexing functional groups of EDTA on the surface, and thus, the formation of Au-CA-EDTA SAM electrode. The new sensor responds to the Pb(2+) and Cu(2+) separately and simultaneously in a wide linear range of concentrations.

Copper(II) nanosensor based on a gold cysteamine self-assembled monolayer functionalized with salicylaldehyde.

Fabrication and electrochemical characterization of a novel nanosensor for determination of Cu2+ in subnanomolar concentrations is described. The sensor is based on gold cysteamine self-assembled monolayer functionalized with salicylaldehyde by means of Schiff's base formation. Cyclic voltammetry, Electrochemical impedance spectroscopy (EIS), and electrochemical quartz crystal microbalance were used to probe the fabrication and characterization of the modified electrode. The sensor was used for quantitative determination of Cu2+ by the EIS in the presence of parabenzoquinone in comparison with stripping Osteryoung square wave voltammetry (OSWV). The attractive ability of the sensor to efficiently preconcentrate trace amounts of Cu2+ allowed a simple and reproducible method for copper determination. A wide range linear calibration curve was observed, 5.0 x 10(-11)-5.0 x 10(-6) and 5.0 x 10(-10)-5.0 x 10(-6) M Cu2+, by using the EIS and OSWV, respectively. Moreover, the sensor presented excellent stability with lower than 10% change in the response, as tested for more than three months daily experiments, and a high repeatability with relative standard deviations of 6.1 and 4.6% obtained for a series of eight successive measurements in 5.0 x 10(-7) M Cu2+ solution, by the EIS and OSWV, respectively.

A novel method for glucose determination based on electrochemical impedance spectroscopy using glucose oxidase self-assembled biosensor.

A method is developed for quantitative determination of glucose using electrochemical impedance spectroscopy (EIS). The method is based on immobilized glucose oxidase (GOx) on the topside of gold mercaptopropionic acid self-assembled monolayers (Au-MPA-GOx SAMs) electrode and mediation of electron transfer by parabenzoquinone (PBQ). The PBQ is reduced to hydroquinone (H(2)Q), which in turn is oxidized at Au electrode in diffusion layer. An increase in the glucose concentration results in an increase in the diffusion current density of the H(2)Q oxidation, which corresponds to a decrease in the faradaic charge transfer resistance (R(ct)) obtained from the EIS measurements. Glucose is quantified from linear variation of the sensor response (1/R(ct)) as a function of glucose concentration in solution. The method is straightforward and nondestructive. The dynamic range for determination of glucose is extended to more than two orders of magnitude. A detection limit of 15.6 microM with a sensitivity of 9.66 x 10(-7) Omega(-1)mM(-1) is obtained.

Application of 2-mercaptobenzothiazole self-assembled monolayer on polycrystalline gold electrode as a nanosensor for determination of Ag(I).

Fabrication and application of a voltammetric sensor based on gold 2-mercaptobenzothiazole self-assembled monolayer (Au-MBT SAM) for determination of silver ion is described. Preliminary experiments were performed to characterize the monolayer. The surface pK(a) determined for the MBT monolayer is 7.0. This value was obtained by impedimetric titration of the monolayer in the presence of Fe(CN)(6)(3-/4-) as a redox probe. The extent of surface coverage was evaluated as 1.52x10(-9)molcm(-2) based on charged consumed for reductive desorption of the monolayer in the 0.50M NaOH solution. Then the sensor was used for determination of Ag(I) by square wave voltammetry. The parameters affecting the sensor response, such as pH and supporting electrolyte, were optimized. A dynamic calibration curve with two linear parts was obtained in the concentration ranges of 5x10(-8)-8x10(-7) and 1x10(-6)-1x10(-5)M of Ag(I). The detection limit adopted from cathodic striping square wave voltammetry was as 1x10(-8)M for n=7. Furthermore, the effect of potential interfering ions on the determination of Ag(I) was studied, and an appropriate method was used for the elimination of this effect.