Amperometric detection of cytochrome c by capillary electrophoresis at a sol–gel carbon composite electrode

Capillary electrophoresis (CE) was employed for the determination of cytochrome c using a wall-jet amperometric detector consisting a copper(I) oxide-modified sol–gel carbon composite electrode (CCE), which exhibits a sensitive electrocatalytic response for the oxidation of cytochrome c. The optimum conditions of separation and detection are 0.08 M NaOH for the separation solution, 12 kV for separation voltage and +0.60 V versus saturated calomel electrode (SCE) for the detection potential. Calibration was linear over the concentration range 1–600 μM with the limit of detection of 3.4 μM, based on a signal-to-noise ratio (S/N) of 3.     

Electrochemical behavior of methyl viologen at graphite electrodes modified with Nafion sol–gel composite

Electrodes were prepared by spin-coating spectroscopic graphite rods with a Nafion doped sol. Coating solutions consisting of Nafion:TEOS (tetraethoxysilane) ratios of 3:1 and 4:1 gave smooth films on the electrode surface. These modified electrodes were evaluated and compared with Nafion modified and bare spectroscopic graphite electrodes using methyl viologen (MV²⁺) as a representative cationic electroactive probe. Substantial partitioning of MV²⁺ into the Nafion:sol–gel matrix to the electrode surface was observed by cyclic voltammetry and square wave voltammetry. Cyclic voltammograms of MV²⁺ in 0.1 M NaCl at Nafion:sol–gel 4:1 modified electrodes showed a reversible reduction to MV⁺ with E^0′=−0.695 V vs. Ag/AgCl. Results of scan rate variation showed the wave to be characterized by semi-infinite diffusion for scan rates in the range 50–500 mV/s. Slowing the scan rate below 50 mV/s resulted in a transition to thin-layer behavior. MV²⁺ partitioned much more quickly into the sol–gel-Nafion modified electrodes compared to pure Nafion modified electrodes. Reversibility of the MV²⁺-loaded modified Nafion-doped sol–gel coatings on electrodes was obtained by soaking in 1 M NaCl solution. Concentration calibration plots for MV²⁺ at the sol–gel-Nafion modified electrodes were nonlinear. Substantial enhancement of current signal at low concentrations was observed by square wave voltammetry.     

Electrocatalytic oxidation of NADH at gold nanoparticles loaded poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) film modified electrode and integration of alcohol dehydrogenase for alcohol sensing

A new modified electrode is fabricated by dispersing gold nanoparticles onto the matrix of poly(3,4-ethylenedioxythiophene)–poly(styrene sulfonic acid), PEDOT–PSS. The electrocatalytic activity of the PEDOT–PSS-Au_nano electrode towards the oxidation of β-nicotinamide adenine dinucleotide (NADH) is investigated. A substantial decrease in the overpotential (>0.7 V) has been observed for the oxidation of NADH at the PEDOT–PSS-Au_nano electrode in comparison to the potential at PEDOT–PSS electrode. The Au nanoparticles dispersed in the PEDOT–PSS matrix prevents the fouling of electrode surface by the oxidation products of NADH and augments the oxidation of NADH at a less positive potential (+0.04 V vs. SCE). The electrode shows high sensitivity to the electrocatalytic oxidation of NADH. Further, the presence of ascorbic acid and uric acid does not interfere during the detection of NADH. Important practical advantages such as stability of the electrode (retains 95% of its original activity after 20 days), reproducibility of the measurements (R.S.D.: 2.8%; n = 5), selectivity and wide linear dynamic range (1–80 μM; R² = 0.996) are achieved at PEDOT–PSS-Au_nano electrode. The ability of PEDOT–PSS-Au_nano electrode to promote the electron transfer between NADH and the electrode makes us to fabricate a biocompatible dehydrogenase-based biosensor for the measurement of ethanol. The biosensor showed high sensitivity to ethanol with rapid detection, good reproducibility and excellent stability.     

Design and application of a flow cell for carbon-film based electrochemical enzyme biosensors

A flow cell has been designed for use with an electrochemical enzyme biosensor, based on low-cost carbon-film electrodes. Three types of mediators were used: cobalt and copper hexacyanoferrates and poly(neutral red) (PNR), covered with glucose oxidase (GOx) immobilised by cross-linking with glutaraldehyde in the presence of bovine serum albumin or inside a oxysilane sol–gel network. Mixtures of sol–gel precursors were made from 3-aminopropyl-triethoxysilane (APTOS) together with methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), tetraethyloxysilane (TEOS) or 3-glycidoxypropyl-trimethoxysilane (GOPMOS), and the best chosen for encapsulation. Optimisation in batch mode, using amperometric detection at fixed potential, showed the PNR-GOx modified carbon-film electrodes to be best for flow analysis for both glutaraldehyde and sol–gel enzyme immobilisation. Both types of enzyme electrode were tested under flow conditions and the reproducibility and stability of the biosensors were evaluated. The biosensors were used for fermentation monitoring of glucose in grape must and interference studies were also performed.     

Evaluation of Meldola Blue‐Carbon Nanotube‐Sol‐Gel Composite for Electrochemical NADH Sensors and Their Application for Lactate Dehydrogenase‐Based Biosensors

A novel MB‐SWNT‐sol‐gel nanocomposite material was prepared by the sol‐gel process incorporating a redox mediator and carbon nanotubes. The electrocatalytic properties of the nanomaterial based sensor toward NADH oxidation were studied by electrochemical measurements. Significant enhancement of oxidation current is obtained at electrodes modified by MB‐SWNT‐sol‐gel in comparison with the analogous carbon black and/or graphite composite modified electrode. The usefulness of the nanocomposite material as a matrix for immobilizing enzymes is also demonstrated. Analytical parameters of D ‐lactate biosensors with and without SWNT in the hybrid film were compared demonstrating that performance of the biosensor was significantly improved when introducing SWNT.     

Microbiosensor for acetylcholine and choline based on electropolymerization/sol–gel derived composite membrane

Amperometric enzyme biosensors for the determination of acetylcholine (ACh) and choline (Ch) have been described. For the fabrication of the biosensors, N-acetylaniline (nAN) was first electropolymerized on a Pt electrode surface to be served as a permselective layer to reject interferences. Bovine serum albumin (BSA) and choline oxidase (CHOD) were co-immobilized in a zinc oxide (ZnO) sol–gel membrane on the above modified Pt electrode for a Ch sensor, or CHOD, acetylcholinesterase (AChE) and BSA immobilized together for an ACh/Ch sensor. The poly (N-acetylaniline) (pnAN) film was the first time used for an ACh/Ch sensor and found to have excellent anti-interference ability, and the BSA in the sol–gel can improve the stability and activity of the enzymes. Amperometric detection of ACh and Ch were realized at an applied potential of +0.6 V versus SCE. The resulting sensors were characterized by fast response, expanded linear range and low interference from endogenous electroactive species. Temperature and pH dependence and stability of the sensor were investigated. The optimal ACh/Ch sensor gave a linear response range of 1.0 × 10⁻⁶ to 1.5 × 10⁻³ M to ACh with a detection limit (S/N = 3) of 6.0 × 10⁻⁷ M and a linear response range up to 1.6 × 10⁻³ M to Ch with a detection limit of 5.0 × 10⁻⁷ M. The biosensor demonstrated a 95% response within less than 10 s.     

An improved bonded-polydimethylsiloxane solid-phase microextraction fiber obtained by a sol-gel/silica particle blend

A novel procedure for solid-phase microextraction fiber preparation is presented, which combines the use of a rigid titanium alloy wire as a substrate with a blend of PDMS sol–gel mixture/silica particles, as a way of increasing both the mechanical robustness and the extracting capability of the sol–gel fibers. The 30 μm average thick fibers displayed an improvement in the extraction capacity as compared to the previous sol–gel PDMS fibers, due to a greater load of stable covalently bonded sol–gel PDMS. The observed extraction capacity was comparable to that of 100 μm non-bonded PDMS fiber, having in this case the advantages of the superior robustness and stability conferred, respectively, by the unbreakable substrate and the sol–gel intrinsic characteristics. Repeatability (n = 3) ranged 1–8% while fiber production reproducibility (n = 3) ranged 15–25%. The presence of the silica particles was found to have no direct influence on the kinetics and mechanism of the extraction process, thus being possible to consider the new procedure as a refinement of the previous ones. The applicability potential of the devised fiber was illustrated with the analysis of gasoline under the context of arson samples.     

Properties of Ce–Zr–La–O nano-system with ruthenium modified surface

Structural peculiarities of Ce–Zr–La–O and Ce–Zr–La–O/Ru samples in mean of catalytic properties are compared. The samples (Ce:Zr = 1:1, La = 10÷30 mol.%, Ru = 1.5 wt.%) were obtained by sol–gel method (X-samples) and co-precipitation (P-samples). It is shown that Ce_0.45Zr_0.45La_0.1O_2−δ/Ru X-samples are characterized by high thermal stability and the highest catalytic activity in partial methane oxidation reaction. According to XRD, BET, FTIR, EPR and XPS data it is concluded that the difference in the samples catalytic activity is caused by various disposition of Ru-containing phase on the support surface. The distinction in the dimension of Ru-containing particles (3D or 2D) is conditioned by structural peculiarities of Ce_0.45Zr_0.45La_0.1O_2−δ and Ce_0.35Zr_0.35La_0.3O_2−δ P- and X-samples.     

Sol–gel immobilized room-temperature phosphorescent metal-chelate as luminescent oxygen sensing material

The chelate formed by 8-hydroxy-7-iodo-5-quinolinesulfonic acid (ferron) with aluminium exhibits strong room-temperature phosphorescence (RTP) when retained on a solid support. In a previous paper we have found that sol–gel technology is a very useful approach for developing RTP optical sensors as a new way to immobilize lumiphors. Sol–gel active phases proved to exhibit a high physical rigidity that enhanced relative RTP intensities and triplet lifetimes of the immobilized probe. In this paper we present an optical sensing phase prepared using the Al–ferron chelate which displays RTP entrapped in a sol–gel glass matrix for the determination of very low levels of oxygen both dissolved in water and organic solvents and in gaseous media. The sol–gel sensing material has proved to be chemically stable for at least 6 months under ambient storage conditions. Besides a high reproducibility in the formation of the sensing materials and no leaching or bleaching of the trapped reagent (neither in the gas phase nor in water or organic solvents) was observed. Oxygen was determined by continuous flow and flow injection methods using both intensity and triplet lifetime measurements. Both methods provided a fast response, good reproducibility and detection limits of 0.0005% (v/v) in the gas phase and <0.01 mg l⁻¹ for dissolved oxygen. An exhaustive study of the effect of some possible interferents present in the gas phase or in solution demonstrated the high specificity of this phosphorescent probe. This highly sensitive oxygen probe has been successfully applied to dissolved oxygen determinations in river and tap waters and its coupling to fiber optics for RTP in-situ monitoring or remote sensing of oxygen has been evaluated.     

Coupled enzyme reaction microarrays based on pin-printing of sol–gel derived biomaterials

We report on the development of a new class of protein microarrays based on the co-immobilization of multiple components within a single pin-printed sol–gel array element. In the first case, the microarraying of a coupled two enzyme reaction involving glucose oxidase and horseradish peroxidase along with the fluorogenic reagent Amplex Red is demonstrated to allow “reagentless” fluorimetric detection of glucose. The second system involved the detection of urea using co-immobilized urease and fluorescein dextran, which works on the basis of a pH induced change in fluorescein emission intensity upon production of ammonium carbonate owing to hydrolysis of urea. In both the cases, it is demonstrated that the changes in intensity from the array are time-dependent, consistent with the enzyme catalyzed reaction, showing that such arrays can be used for kinetic studies. The rate of intensity change was also found to be dependent on the concentration of analyte added to the array, showing that such arrays could be useful for quantitative multianalyte biosensing. Inhibition of urease by the competitive inhibitor thiourea is also demonstrated on a microarray, demonstrating that sol–gel-based microarrays may find use in high-throughput drug-screening applications.     

Sol–gel encapsulated cobalt(III) acetylacetonate for air oxidation of penicillin derivatives

The sulfoxides of penicillin derivatives are important pharmaceutical intermediates and can be prepared by air oxidation of corresponding sulfides catalyzed by cobalt(III) acetylacetonate (Co(acac)₃). However, when using the homogeneous catalyst, it is very difficult to separate the catalyst from product, which makes it impossible to reuse the catalyst directly. While the heterogeneous Co(acac)₃ encapsulated by sol–gel method can solve the problem. They have high selectivity and activity. They are leach proof and can be recycled in numerous runs. The sol–gel precursor can be tetraethoxysilane (TEOS) or tetrabutyl titanate (TBOTi) or triisopropyl aluminate (TIOAl). FT-IR and N₂ adsorption was employed to characterize the sol–gel catalyst. HPLC was used to analyze the conversion of penicillin derivatives.     

Low Potential Detection of NADH at Titanium‐Containing MCM‐41 Modified Glassy Carbon Electrode

Titanium‐containing MCM‐41 (Ti‐MCM‐41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of β‐Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the over‐voltage of NADH oxidation reaction is observed at 0.28 V (vs. SCE). The modified electrode is found to be stable and reproducible. The electrode shows a linear response for a wide range of 10–1200 μM NADH and the detection limit is 8.0 μM. Ti‐MCM‐41 mesoporous molecular sieves provide an efficient matrix for development of NADH biosensors and the prepared electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix of the construction of dehydrogenases biosensor.     

Electrocatalytic oxidation of NADH at mesoporous carbon modified electrodes

The electrochemical oxidation of β-nicotinamine adenine dinucleotide (NADH) was investigated at a glassy carbon electrode modified with carbon mesoporous materials (CMM). Due to the large surface area and electro-catalytic properties of CMM, the overpotential of the electrodes toward the oxidation of NADH is decreased by 595 mV in aqueous solution at neutral pH. The anodic peak currents increase steadily with the concentration of NADH in the range from 2 µM to 1.1 mM, the detection limit being 1.0 µM at pH 7.2 and a potential of +0.3 V vs. SCE. The apparent Michaelis-Menten constant is ～21.5 μM. The results enable NADH to be sensed at a low potential and are promising with respect to the design of dehydrogenase-based amperometric biosensors.     

Carbon nanofiber vs. carbon microparticles as modifiers of glassy carbon and gold electrodes applied in electrochemical sensing of NADH

Carbon materials (CMs), such as carbon nanotubes (CNTs), carbon nanofibers (CNFs), and carbon microparticles (CMPs) are used as doping materials for electrochemical sensors. The efficiency of these materials (either before or after acidic treatments) while being used as electrocatalysts in electrochemical sensors is discussed for β-nicotinamide adenine dinucleotide (NADH) detection using cyclic voltammetry (CV). The sensitivity of the electrodes (glassy carbon (GC) and gold (Au)) modified with both treated and untreated materials have been deeply studied. The response efficiencies of the GC and Au electrodes modified with CNF and CMP, using dimethylformamide (DMF) as dispersing agent are significantly different due to the peculiar physical and chemical characteristics of each doping material. Several differences between the electrocatalytic activities of CMs modified electrodes upon NADH oxidation have been observed. The CNF film promotes better the electron transfer of NADH minimizing the oxidation potential at +0.352 V. Moreover higher currents for the NADH oxidation peak have been observed for these electrodes. The shown differences in the electrochemical reactivities of CNF and CMP modified electrodes should be with interest for future applications in biosensors.     

Headspace solid-phase microextraction with novel sol–gel permethylated-β-cyclodextrin/hydroxyl-termination silicone oil fiber for determination of polybrominated diphenyl ethers by gas chromatography–mass spectrometry in soil

A simple, sensitive, and accurate method for determination of polybrominated diphenyl ethers (PBDEs) in soil has been developed based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry (GC–MS). Permethylated-β-cyclodextrin/hydroxyl-termination silicone oil (PM-β-CD/OH-TSO) fiber was first prepared by sol–gel technology and employed in SPME procedure. By exploiting the superiorities of sol–gel coating technique and the advantages of the high hydrophobic doughnut-shaped cavity of PM-β-CD, the novel fiber showed desirable operational stability and extraction ability. After optimization on extraction conditions like water addition, extraction temperature, extraction time, salts effect, and solvents addition, the method was validated in soil samples, achieving good linearity (r > 0.999), precision (R.S.D. < 10%), accuracy (recovery > 78%), and detection limits (S/N = 3) raging from 13.0 to 78.3 pg/g.     

TPR/TPO characterization of cobalt–silicon mixed oxide nanocomposites prepared by sol–gel

Cobalt–silicon mixed oxides with Co/Si ratio of 10/90 (10Co), 20/80 (20Co) and 30/70 (30Co) were prepared by a modified sol–gel method. The materials treated in air at 400 and 600 °C were characterized by SEM and TPR/TPO techniques. TPR measurements showed that in all samples only a fraction of Co was present as Co₃O₄ and as amorphous silicate and was reducible by H₂ within 800 °C, while a part was not reducible under TPR conditions. The fraction of Co not reducible decreased with increasing Co content. A TPO/TPR cycle gave rise to an increase of the fraction of not reducible Co.     

Sol–gel synthesis and crystallisation of 3CaO·2SiO2 glassy powders

A gel of composition 3CaO·2SiO₂ was synthesised by means of sol–gel route involving hydrolysis of tetramethyl orthosilicate (TMOS) with calcium nitrate in alcoholic medium, and polycondensation reaction. The gel was submitted to DTA and TGA analysis and the resulted material was examined by FTIR spectroscopy and X-ray powder diffractometry. The thermal treatments required for the gel into glass conversion led to a partially devitrified product. The XRD analysis showed that the structure obtained is highly depolymerised.     

A flow injection method for the analysis of tetracycline antibiotics in pharmaceutical formulations using electrochemical detection at anodized boron-doped diamond thin film electrode

A method using flow injection (FI) with amperometric detection at anodized boron-doped diamond (BDD) thin films has been developed and applied for the determination of tetracycline antibiotics (tetracycline, chlortetracycline, oxytetracycline and doxycycline). The electrochemical oxidation of the tetracycline antibiotics was studied at various carbon electrodes including glassy carbon (GC), as-deposited BDD and anodized BDD electrodes using cyclic voltammetry. The anodized BDD electrode exhibited well-defined irreversible cyclic voltammograms for the oxidation of tetracycline antibiotics with the highest current signals compared to the as-deposited BDD and glassy carbon electrodes. Low detection limit of 10 nM (signal-to-noise RATIO = 3) was achieved for each drug when using flow injection analysis with amperometric detection at anodized BDD electrodes. Linear calibrations were obtained from 0.1 to 50 mM for tetracycline and 0.5–50 mM for chlortetracycline, oxytetracycline and doxycycline. The proposed method has been successfully applied to determine the tetracycline antibiotics in some drug formulations. The results obtained in percent found (99.50–103.01%) were comparable to dose labeled.     

Detection of NADH and Ethanol at Titanium Containing MCM‐41 with Low Overpotential

Titanium‐containing MCM‐41 (Ti‐MCM‐41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of β‐Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the overvoltage of NADH oxidation reaction is observed at 0.28 V vs. SCE. The application in the amperometric biosensing of ethanol using alcohol dehydrogenase enzyme (ADH) also has been demonstrated with this material. The proposed sensor shows a highly sensitivity, an acceptable reproducibility and a good stability. The linear range of ethanol is 25–1000 μM and the detection limit is 8.0 μM. Ti‐MCM‐41 modified electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix for the construction of dehydrogenases sensor.     

A photocatalytic membrane reactor for VOC decomposition using Pt-modified titanium oxide porous membranes

Porous titanium oxide membranes with pore sizes in the range of 2.5–22 nm were prepared by a sol–gel procedure, and were applied for decomposition of methanol and ethanol as model volatile organic compounds (VOCs) in a photocatalytic membrane reactor, where oxidation reaction occurs both on the surface and inside the porous TiO₂ membrane while reactants are permeating via one-pass flow. Methanol was completely photo-oxidized by black-light irradiation to CO₂ when methanol at a concentration of 100 ppm was used at a feed flow rate of 500 × 10⁻⁶ m³/min, but the conversion decreased when the MeOH concentration in the feed was increased. Pt-modification was carried out by photo-deposition, and led to a decrease in pore diameter. Using Pt-modified membranes, a nearly complete oxidation of methanol up to 10,000 ppm at a feed flow rate of 500 × 10⁻⁶ m³/min was observed. Thus, such membranes would be effective for purifying a permeate stream after one-pass permeation through the TiO₂ membranes. The decomposition of ethanol is also discussed.