Development of an optical sensor for determination of zinc by application of PC-ANN

A very sensitive and reversible optical chemical sensor based on dithizone as chromoionophore immobilized within a plasticized carboxylated PVC film for Zn²⁺ determination is described. At optimum conditions (i.e. pH 5.0), the proposed sensor displays a linear response to Zn²⁺ over 5.0 × 10⁻⁸-5.0 × 10⁻⁶ mol L⁻¹ range. This range was improved to 2.5 × 10⁻⁸-5.8 × 10⁻⁵ mol L⁻¹ range by applying principle component-feed forward artificial neural network with back-propagation training algorithm (PC-ANNB). Detection limit of 8.0 × 10⁻⁹ mol L⁻¹ was obtained. The sensor is fully reversible within the dynamic range and the response time (t_95%) is approximately 4 min under batch conditions. In addition to its high stability and reproducibility, the sensor shows good selectivity towards Zn²⁺ ion with respect to common metal cations. The sensor was successfully applied for determination of Zn²⁺ ion in hair sample.     

A sensitive hydrazine electrochemical sensor based on electrodeposition of gold nanoparticles on choline film modified glassy carbon electrode

A highly sensitive hydrazine sensor was developed based on the electrodeposition of gold nanoparticles onto the choline film modified glassy carbon electrode (GNPs/Ch/GCE). The electrochemical experiments showed that the GNPs/Ch film exhibited a distinctly higher activity for the electro-oxidation of hydrazine than GNPs with 3.4-fold enhancement of peak current. The kinetic parameters such as the electron transfer coefficient (α) and the rate of electron exchange (k) for the oxidation of hydrazine were determined. The diffusion coefficient (D) of hydrazine in solution was also calculated by chronoamperometry. The sensor exhibited two wide linear ranges of 5.0 × 10⁻⁷-5.0 × 10⁻⁴ and 5.0 × 10⁻⁴-9.3 × 10⁻³ M with the detection limit of 1.0 × 10⁻⁷ M (s/n = 3). The proposed electrode presented excellent operational and storage stability for the determination of hydrazine. Moreover, the sensor showed outstanding sensitivity, selectivity and reproducibility properties. All the results indicated a good potential application of this sensor in the detection of hydrazine.     

Simultaneous determination of N-acetylcysteine and acetaminophen by voltammetric method using N-(3,4-dihydroxyphenethyl)-3,5-dinitrobenzamide modified multiwall carbon nanotubes paste electrode

A new dopamine-derivative, i.e. N-(3,4-dihydroxyphenethyl)-3,5-dinitrobenzamide (N-DHPB), was synthesized and its application was investigated for the simultaneous determination of N-acetylcysteine (NAC) and acetaminophen (AC) using modified multiwall carbon nanotubes paste electrode. This modified electrode exhibited a potent and persistent electron mediating behavior followed by well separated oxidation peaks of NAC and AC. The peaks current of differential pulse voltammograms of NAC and AC increased linearly with their concentration in the ranges of 0.5-200 μmol L⁻¹ NAC and 15.0-270 μmol L⁻¹ AC. The detection limits for NAC and AC were 0.2 μmol L⁻¹ and 10.0 μmol L⁻¹, respectively. The relative standard deviation for seven successive assays of 1.0 and 30.0 μmol L⁻¹ NAC and AC were 1.7% and 2.2%, respectively. The proposed sensor was successfully applied for the determination of NAC in human urine, tablet, and serum samples.     

Aptamer-based colorimetric biosensing of dopamine using unmodified gold nanoparticles

A simple, sensitive and selective colorimetric biosensor for the detection of dopamine (DA) was demonstrated with a 58-mer dopamine-binding aptamer (DBA) as recognition element and unmodified gold nanoparticles (AuNPs) as probes. Upon the addition of DA, the conformation of DBA would change from a random coil structure to a rigid tertiary structure like a pocket and this change has been demonstrated by circular dichroism spectroscopic experiments. Besides, the conformational change of DBA could facilitate salt-induced AuNP aggregation and lead to the color change of AuNPs from red to blue. The calibration modeling showed that the analytical linear range covered from 5.4 × 10⁻⁷ M to 5.4 × 10⁻⁶ M and the corresponding limit of detection (LOD) was 3.6 × 10⁻⁷ M. Some common interferents such as 3,4-dihydroxyphenylalanine (DOPA), catechol, epinephrine (EP), 3,4-dihydroxyphenylacetic acid (DOPAC), homovanillic acid (HVA), and ascorbic acid (AA) showed no or just a little interference in the determination of DA.     

Two-dimensional molecular imprinting approach for the electrochemical detection of trinitrotoluene

In this work, we demonstrated a sensitive and selective electrochemical sensing protocol for the detection of TNT prepared from alkanethiols self-assembled on AuNPs modified glassy carbon (GC) electrode with preadsorbed templates of TNT. It demonstrated that the 2D molecular imprinting monolayers (MIMs) can provide a better site accessibility and lower mass-transfer resistance, while the AuNPs can enhance electrode conductivity, facilitate the electron transfer and increase the amount of TNT-imprinted sites. The prepared sensor showed not only high selectivity toward TNT in comparison to other similar nitroaromatic compounds (NACs), but also a wide linear range over TNT concentration from 4.0 × 10⁻⁸ to 3.2 × 10⁻⁶ M with a detection limit of 1.3 × 10⁻⁸ M (S/N = 3). Moreover, the imprinted sensor has been applied to the determination of TNT in spiked environmental water samples and shows promise for fast and sensitive measurement of trace levels of TNT in real samples.     

Direct electrochemistry of cytochrome P450 6A1 in mimic bio-membrane and its application for pesticides sensing

The direct electrochemistry of house fly cytochrome P4506A1 (CYP6A1) confined in dioctadecyl dimethyl ammonium bromide (DDAB) film was achieved. The immobilized CYP6A1 displayed a pair of redox peaks with a formal potential of −0.36 mV in pH 7.0 O₂-free phosphate buffers at scan rate of 1 V s⁻¹ and the direct electron transfer of CYP6A1 was characterized by voltammetry. The CYP6A1 in the DDAB film retained its bioactivity and could catalyze the reduction of dissolved oxygen. Upon addition of its substrate aldrin or heptachlor to the air-saturated solution, the reduction peak current of dissolved oxygen increased, which indicates the catalytic behavior of CYP6A1 to its substrates. By amperometry a calibration linear range was obtained to be 9.08 × 10⁻⁶-4.54 × 10⁻⁵ mol L⁻¹ with a sensitivity of 80 μA mM⁻¹ for aldrin or 8.91 × 10⁻⁶-4.46 × 10⁻⁵ mol L⁻¹ with a sensitivity of 66 μA mM⁻¹ for heptachlor. The apparent Michaelis-Menten constant for the electrocatalytic activity of CYP6A1 was found to be 7.468 × 10⁻⁵ mol L⁻¹ for aldrin and 4.316 × 10⁻⁵ mol L⁻¹ for heptachlor. The bioelectrocatalytic products were analysed using gas chromatography (GC) and electron ionization-mass spectrometry (EI-MS). The results confirmed that epoxidation was the main pathways of CYP6A1-mediated organochlorine pesticides oxidation.     

Screen-printed carbon electrode for choline based on MnO2 nanoparticles and choline oxidase/polyelectrolyte layers

This paper presents the amperometric biosensor that determines choline and cholinesterase activity using a screen printed graphite electrode. In order to detect H₂O₂ we have blanket modified the electrode material with manganese dioxide nanoparticles layer. Using layer-by-layer technique on the developed hydrogen peroxide sensitive electrode surface choline oxidase was incorporated into the interpolyelectrolyte nanofilm. Its ability to serve as a detector of choline in bulk analysis and cholinesterase assay was investigated. We examined the interferences from red-ox species and heavy metals in the blood and in the environmental sample matrixes. The sensor exhibited a linear increase of the amperometric signal at the concentration of choline ranging from 1.3 × 10⁻⁷ to 1.0 × 10⁻⁴ M, with a detection limit (evaluated as 3σ) of 130 nM and a sensitivity of 103 mA M⁻¹ cm⁻² under optimized potential applied (480 mV vs. Ag/AgCl). The biosensor retained its activity for more than 10 consecutive measurements and kept 75% of initial activity for three weeks of storage at 4 °C. The R.S.D. was determined as 1.9% for a choline concentration of 10⁻⁴ M (n = 10) with a typical response time of about 10 s. The developed choline biosensor was applied for butyrylcholinesterase assay showing a detection limit of 5 pM (3σ). We used the biosensor to develop the cholinesterase inhibitor assay. Detection limit for chlorpyrifos was estimated as 50 pM.     

Electrocatalytic determination of hydrazine by a glassy carbon electrode modified with PEDOP/MWCNTs-Pd nanoparticles

The electrocatalysis of hydrazine oxidation by poly-ethylenedioxy pyrrole (PEDOP)-coated MWCNTs-palladium nanoparticles [PEDOP/MWCNTs-Pd] was investigated as an electrochemical sensor on the surface of glassy carbon electrode (GCE) in aqueous medium. Electrochemical oxidation of hydrazine in phosphate buffer (pH 7.4) was performed using cyclic voltammetry (CV) and chronoamperometry (CA) methods. Using the proposed electrode, the catalytic oxidation peak current of hydrazine was high and the overpotential of its oxidation decreased. Based on the obtained results, a mechanism for electrooxidation of hydrazine at [PEDOP/MWCNTs-Pd/GCE] demonstrated an irreversible diffusion-controlled electrode process and a four-electron transfer involved in the overall reaction. The experimental results showed that the mediated oxidation peak currents of the hydrazine were linearly dependent on the concentration of hydrazine in the range of 1.0 × 10⁻⁷ to 5.0 × 10⁻³ M. The detection limit (S/N = 3) was found to be 4 × 10⁻⁸ M with a fast response time of 10 s.     

Direct oxidation of methionine at screen printed graphite macroelectrodes: Towards rapid sensing platforms

The direct electrochemical oxidation of methionine has been achieved at bare carbon based electrodes and for the first time at screen printed graphite electrodes in aqueous solutions. Due to scales of economy and intended use as a potential point-of-care sensor, the quantification of methionine was explored at screen printed electrodes, allowing linear ranges over the range 0.05-5.0 mM with a detection limit of 95 × 10⁻⁶ mol L⁻¹ possible in model solutions. Application of this sensor was used for the determination of methionine in a pharmaceutical product containing a complex mixture of vitamins, amino acids, chelated minerals and additional factors with the results agreeing with manufacturers’ specification suggesting that this sensing platform holds promise as a rapid, sensitive and disposable sensor for methionine determination.     

Red tide detection and tracing using MODIS fluorescence data: A regional example in SW Florida coastal waters

Near real-time data from the MODIS satellite sensor was used to detect and trace a harmful algal bloom (HAB), or red tide, in SW Florida coastal waters from October to December 2004. MODIS fluorescence line height (FLH in W m^− 2 μm^− 1 sr^− 1) data showed the highest correlation with near-concurrent in situ chlorophyll-a concentration (Chl in mg m^− 3). For Chl ranging between 0.4 to 4 mg m^− 3 the ratio between MODIS FLH and in situ Chl is about 0.1 W m^− 2 μm^− 1 sr^− 1 per mg m^− 3 chlorophyll (Chl = 1.255 (FLH × 10)^0.86, r = 0.92, n = 77). In contrast, the band-ratio chlorophyll product of either MODIS or SeaWiFS in this complex coastal environment provided false information. Errors in the satellite Chl data can be both negative and positive (3-15 times higher than in situ Chl) and these data are often inconsistent either spatially or temporally, due to interferences of other water constituents. The red tide that formed from November to December 2004 off SW Florida was revealed by MODIS FLH imagery, and was confirmed by field sampling to contain medium (10⁴ to 10⁵ cells L^− 1) to high (> 10⁵ cells L^− 1) concentrations of the toxic dinoflagellate Karenia brevis. The FLH imagery also showed that the bloom started in mid-October south of Charlotte Harbor, and that it developed and moved to the south and southwest in the subsequent weeks. Despite some artifacts in the data and uncertainty caused by factors such as unknown fluorescence efficiency, our results show that the MODIS FLH data provide an unprecedented tool for research and managers to study and monitor algal blooms in coastal environments.     

Electrochemical genosensor based on modified octadecanethiol self-assembled monolayer for Escherichia coli detection

An electrochemical genosensor based on 1-fluoro-2-nitro-4-azidobenzene (FNAB) modified octadecanethiol (ODT) self-assembled monolayer (SAM) has been fabricated for Escherichia coli detection. The results of electrochemical response measurements investigated using methylene blue (MB) as a redox indicator reveal that this nucleic acid sensor has 60 s of response time, high sensitivity (0.5 × 10⁻¹⁸ M) and linearity as 0.5 × 10⁻¹⁸-1 × 10⁻⁶ M. The sensor has been found to be stable for about four months and can be used about ten times. It is shown that water borne pathogens like Klebsiella pneumonia, Salmonella typhimurium and other gram-negative bacterial samples has no significant effects in the response of this sensor.     

Rapid parallelized and quantitative analysis of five pathogenic bacteria by ITS hybridization using QCM biosensor

We developed a 2 × 5 model quartz crystal microbalance (QCM) DNA biosensor array for detection of five bacteria, which based on hybridization analysis of bacterial 16S-23S rDNA internal transcribed spacer (ITS) region. A pair of universal primers was designed for PCR amplification of the ITSs. The PCR products were analyzed by the biosensor. We used gold nanoparticles to amplify the frequency shift signals. Fifty clinical samples were detected by both the biosensor and conventional bacteria culture method. We found a linear quantitative relationship between frequency shift and logarithmic concentration of synthesized oligonucleotides or bacteria cells. The measurable concentration ranged from 10⁻¹² to 10⁻⁸ M for synthesized oligonucleotides and 1.5 × 10² to 1.5 × 10⁸ CFU/mL for bacteria. The 10⁻¹² M of synthesized oligonucleotides or 1.5 × 10² CFU/mL of Pseudomonas aeruginosa could be detected by the biosensor system. The detection could be completed within 5 h including the PCR amplification procedure. Compared with bacteria culture method, the detection sensitivity and specificity of the biosensor system were 94.12% and 90.91%, respectively. There was no significant difference between these two methods (P = 0.625 > 0.05). The biosensor system provides a rapid and sensitive method for parallelized and quantitative analysis of multiple pathogenic bacteria in clinical diagnosis.     

Electrochemical studies of bovine serum albumin immobilization onto the poly-o-phenylenediamine and carbon-coated nickel composite film and its interaction with papaverine

A biosensor based on bovine serum albumin (BSA) and poly-o-phenylenediamine (PoPD)/carbon-coated nickel (C-Ni) nanobiocomposite film modified electrode has been developed to study the interaction of BSA with papaverine (PAP). The well-dispersed C-Ni nanoparticles were dripped onto the glassy carbon electrode (GCE) surface firstly, and PoPD films were subsequently electropolymerized by cyclic voltammetry (CV) to prepare PoPD/C-Ni/GCE. Finally, the BSA was easily immobilized on the PoPD films via electrostatic adsorption. The morphology and the electrochemical properties of the fabricated composite electrodes were examined by scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS), respectively. The interaction of PAP with BSA was monitored by differential pulse voltammetry (DPV), using PoPD as the electrochemical indicator. The binding constant (K), obtained by DPV, was 1.7 × 10⁴ L/mol, which was consistent with the fluorescence analysis. This constructed biosensor also exhibited a fine linear correlation with PAP concentration range of 2.5 × 10⁻⁹-4.5 × 10⁻⁵ mol/L and a detection limit of 8.3 × 10⁻¹⁰ mol/L was achieved by DPV.     

Biomonitoring of methomyl pesticide by laccase inhibition on sensor containing platinum nanoparticles in ionic liquid phase supported in montmorillonite

This study focuses on the development and evaluation of a new biosensor for the determination of the pesticide methomyl, based on enzyme inhibition. Laccase (LAC) obtained from a genetically modified fungus (Aspergillus oryzae) was successfully immobilized in a new supported ionic liquid phase (SILP) based on platinum nanoparticles and the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (Pt-BMI·BF₄) supported in montmorillonite, and subsequently applied in the construction of the biosensor. The process of inhibition by methomyl carbamate was performed using dopamine as a phenolic substrate to obtain the base signal. All measurements for the optimization and application of the biosensor were performed by square-wave voltammetry, and the best experimental conditions were obtained in acetate buffer solution (0.1 mol L⁻¹, pH 5.5), with 0.5 units of enzyme and voltammetric parameters: 60 Hz of frequency, 100 mV of pulse amplitude and 8 mV of scan increment. The determination of methomyl in carrot and tomato samples using the proposed biosensor showed results consistent with those obtained by HPLC, verifying that the method developed can be used for the quantification of this pesticide.     

The m-pancycle-connectivity of a WK-Recursive network

In this paper, we study the m-pancycle-connectivity of a WK-Recursive network. We show that a WK-Recursive network with amplitude W and level L is strictly (5 × 2^L−1 − 2)-pancycle-connected for W ? 3. That is, each pair of vertices in a WK-recursive network with amplitude greater than or equal to 3 resides in a common cycle of every length ranging from 5 × 2^L−1 − 2 to N, where N is the size of the interconnection network; and the value 5 × 2^L−1 − 2 reaches the lower bound of the problem.     

High sensitive optode for selective determination of Ni based on the covalently immobilized thionine in agarose membrane

A novel Ni²⁺ optode was prepared by covalent immobilization of thionine, 3,7-diamine-5-phenothiazoniom thionineacetate, in a transparent agarose membrane. Influences of various experimental parameters on Ni²⁺ sensing, including the reaction time, the solution pH and the concentration of reagents were investigated. Under the optimized conditions, a linear response was obtained for Ni²⁺ concentrations ranging from 1.00 × 10⁻¹⁰ to 1.00 × 10⁻⁷ mol l⁻¹ with an R² value of 0.9985. The detection limit (3σ) of the method for Ni²⁺ was 9.30 × 10⁻¹¹ mol l⁻¹. The influence of several potentially interfering ions such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Pb²⁺, Cu²⁺, Mn²⁺, Co³⁺, Cr³⁺, Al³⁺ and Fe³⁺ on the determination of Ni²⁺ was studied and no significant interference was observed. The membrane showed a good durability and short response time with no evidence of reagent leaching. The membrane was successfully applied for the determination of Ni²⁺ in environmental water samples.     

An acoustic wave sensor for the hydrophilic fluoride

A new acoustic wave sensor to detect and quantify fluoride, one of the most hydrophilic anions, is proposed. Meso-octamethylcalix[4]pyrrole (OMCP) and seven of its derivatives were evaluated as piezoelectric quartz crystal coatings. Some of these sensors experienced appreciable coating leaching under a water flow, while others did show a very small sensitivity to fluoride. As the OMCP-naphthoquinone sensor was very sensitive to fluoride and did not lose a significant amount (α = 0.05) of coating during eight weeks, it was selected among all the others. A piezoelectric crystal coated with an amount of OMCP-naphthoquinone that produced a frequency decrease of 22 kHz showed a linear calibration range that extended up to 80 mg L⁻¹, within which sensitivity to fluoride was 0.45 Hz L mg⁻¹_, and was able to detect fluoride at the concentration of 3.66 mg L⁻¹. This sensor was used to determine fluoride in commercial fluoride tablets, and the result found was not statistically different (α = 0.05) from the value provided by the manufacturer.     

Aptamer biosensor for label-free impedance spectroscopy detection of thrombin based on gold nanoparticles

This paper presents a simple electrochemical impedance spectroscopy (EIS) aptasensor based on an anti-thrombin-aptamer as a molecular recognition element. Improvement in sensitivity was achieved by utilizing gold nanoparticles (AuNPs), which were self-assembled on the surface of a bare electrode by using 1,6-Hexanedithiol as a medium. To quantify the amount of thrombin, changes in the interfacial electron transfer resistance (R_et) of the aptasensor were monitored using the redox couple of an [Fe(CN)₆]^3−/4− probe. The plot of (Reti−Ret₀)/Ret₀ against the logarithm of thrombin concentration is linear with over the range from 0.1 nM to 30 nM with a detection limit of 0.013 nM. Meanwhile, the packing density of aptamers was determined by cyclic voltammetric (CV) studies of redox cations (e.g., [Ru(NH₃)₆]³⁺) which were electrostatically bound to the DNA phosphate backbones. The results indicate that the total amount of aptamer probes immobilized on the gold nanoparticle surface is sixfold higher than that on the bare electrode. The aptasensor also showed good selectivity for thrombin without being affected by the presence of other proteins.     

A label-free amperometric immunosensor based on horseradish peroxidase functionalized carbon nanotubes and bilayer gold nanoparticles

In this work, a novel label-free amperometric immunosensor has been constructed for detecting α-1-fetoprotein (AFP) based on nanocomposite of horseradish peroxidase (HRP) labeled carbon nanotubes (CNTs). First, the gold nanoparticles (AuNPs) were electrodeposited on the surface of the glass carbon electrode by electrochemical reduction of gold chloride tetrahydrate (HAuCl₄) to immobilize horseradish peroxidase labeled carbon nanotubes (HRP-CNTs). Then HRP-CNTs bioconjugate was immobilized on the surface of the electrodeposited AuNPs layer by the combination of forces (coordination and electrostatic force). Subsequently, it was immersed into gold colloidal nanoparticles (GNPs) solution, which was used to immobilize antibody biomolecules (anti-AFP). Enhanced sensitivity was obtained by using bioconjugates featuring HRP labeled (HRP-CNTs), which had lager specific surface area and good electronic catalysis (current response signal) compared to carbon nanotubes. Under optimized conditions, the linear ranges were from 0.2 to 200 ng mL⁻¹ with a detection limit of 0.067 ng mL⁻¹ (at an S/N of 3). The proposed immunosenor showed good precision, acceptable stability and reproducibility and could be used for the detection AFP in normal human serum, which provided a potential alternative tool for the detection of protein in clinical diagnosis.     

Graphite oxide film-modified electrode as an electrochemical sensor for acetaminophen

The graphite oxide (GO) was prepared via the chemical oxidation of natural graphite powder, and then used to modify the surface of glassy carbon electrode (GCE). The electrochemical behavior of acetaminophen was examined. In 0.01 mol L⁻¹ HCl, an irreversible oxidation peak is observed for acetaminophen, and the peak current remarkably increases at the GO film-modified GCE. The influences of supporting electrolyte, amount of GO suspension, accumulation potential and time were studied on the oxidation peak current of acetaminophen. As a result, a new electrochemical method was developed for the detection of acetaminophen. The linear range is from 25 μg L⁻¹ to 4 mg L⁻¹, and the limit of detection is 6 μg L⁻¹ based on three signal-noise ratio. Finally, it was successfully used to detect acetaminophen in tablets.