A visualization method for quickly detecting nitrite ions in breath condensate using a portable closed bipolar electrochemical sensor.

A portable and non-invasive sensor presents an innovative way to measure inflammation biomarkers in exhaled breath condensate (EBC). This research is focused on developing a miniaturized bipolar electrochemical sensor that can be connected to a smartphone app. This device will be able to detect adding known amounts of nitrite (spikes) to a salt solution and small amounts of nitrite ions in collected real samples in EBC. The sensor was fabricated and tested for its rapid electron transfer capability and ability to detect nitrite ions even at very low concentrations and low real sample levels. In the proposed setup, when the required potential was applied by using a direct power supply, the nitrite ions were oxidized electrocatalytically at amine-functionalized graphene oxide (AGO) decorated with gold nanoparticles on a carbon paper anodic pole. On the other hand, the reduction reaction of Prussian blue occurred at the cathodic pole of the bipolar electrode simultaneously. This strategy led to a change in color from blue to white as a result of the reduction process and the color change is proportional to the concentration of nitrite ions in the analytical solution. The combination of smartphones with the colorimetric method has resulted in a platform for the detection of test strips that is more visual and convenient. The amperometry and voltammetric methods of nitrite detection showed a linear range of up to 1230 µM. The bipolar electrochemical sensor was able to detect the clinically relevant range of nitrite from 0.5 to 85 µM in a buffer with an ultralow detection limit (LOD) of 250 nM (S/N = 3), fast response and excellent selectivity. It was benchmarked by utilizing pre-characterized real EBC samples to differentiate patients with respiratory diseases from healthy volunteers. By tracking the results of nitrite measurements over time, it has become possible to detect trends and changes in an individual's nitrite ion concentration and to potentially identify lung inflammation earlier.

Nitrone Synthesis via Pair Electrochemical Coupling of Nitro-Compounds with Benzyl Alcohol Derivatives.

Here we report a paired electrochemical coupling of readily accessible nitro-compounds with benzyl alcohols to yield nitrone derivatives. In this work, electrochemical behavior of nitrobenzene and benzyl alcohol derivatives was studied by cyclic voltammetry and controlled potential coulommetry. Electrochemical reactions have been performed in aqueous/ethanol (or acetonitrile) solutions by employing common graphite electrodes and a simple controlled current protocol which can make this strategy more appealing than other conventional pathways.

Synergistic effect of magnetite and gold nanoparticles onto the response of a label-free impedimetric hepatitis B virus DNA biosensor.

A magnetite and gold nanoparticle modified carbon paste electrode (CPE) was prepared for the immobilization of a thiol modified Hepatitis B virus (HBV) probe DNA and determination trace amount of target HBV DNA. Indeed, the sensing platform integrated two nanoparticles that had previously been employed individually in the DNA biosensors. The proposed DNA biosensor could measure target HBV DNA virus concentration with a low detection limit of 3.1 (±0.1)×10-(13)M, which was greatly lower than the detection limit reported with gold or magnetite nanoparticles alone. The change of interfacial charge transfer resistance (RCT) was confirmed the hybrid formation between probe and target HBV DNA. The RCT difference (before and after hybridization with the target HBV DNA) was in a linear relationship with the logarithm of complementary oligonucleotide concentrations in the range of 8.3 (±0.1)×10(-13) to 6.4 (±0.2)×10(-7)M. In addition, the novel methodology for specific DNA sequence detection was highly selective, repeatable, and reproducible. Finally, this work was successfully utilized for the sensitive and label free impedimetric determination of HBV target DNA in the urine and blood plasma samples.

A novel morphine electrochemical biosensor based on intercalative and electrostatic interaction of morphine with double strand DNA immobilized onto a modified Au electrode.

The intercalative and electrostatic interaction of morphine with double-stranded DNA (ds-DNA), which was immobilized onto mercapto-benzaldehyde-modified Au electrode, was employed for designing a sensitive biosensor. The interaction of morphine with the immobilized ds-DNA onto the electrode surface has been studied by differential pulse voltammetry (DPV). Under the optimum conditions, a linear dependence for the morphine concentration in the range of 0.05-500 µmol L(-1) and its oxidation signal were observed and a detection limit of 0.01 µmol L(-1) for the morphine was obtained. The reproducibility and applicability of the analysis to real samples were also investigated and results demonstrated that this DNA biosensor could be utilized for the sensitive, rapid, simple, and cost effective determination of morphine in urine and blood plasma samples.

Development of a novel MWCNTs-triazene-modified carbon paste electrode for potentiometric assessment of Hg(II) in the aquatic environments.

In this approach, a new chemically modified carbon paste electrode was assembled for potentiometric assay of mercury(II) ion in the aqueous environments. Hereby, MWCNTs were used in the carbon paste composition to meliorate the electrical conductivity and sensitivity of the carbon paste owing to its exceptional physicochemical characteristics. Likewise, participation of the BEPT as a super-selective ionophore in the carbon paste composition boosted significantly the selectivity of the modified electrode towards Hg(II) ions over a wide concentration range of 4.0 × 10(-9)-2.2 × 10(-3) mol L(-1) with a lower detection limit of 3.1 × 10(-9) mol L(-1). Besides, Nernstian slope of the proposed sensor was 28.9(± 0.4)mV/decade over a pH range of 3.0-5.2 with potentiometric short response time of 10s. In the interim, by storing in the dark and cool dry place during non-usage period, the electrode can be used for at least 30 days without any momentous divergence of the potentiometric response. Eventually, to judge about its practical efficiency, the arranged sensor was utilized successfully as an indicator electrode for potentiometric titration of mercury(II) with standard solution of EDTA. As well, the quantitative analysis of mercury(II) ions in some aqueous samples with sensible accuracy and precision was satisfactorily performed.

Magnetic pH-responsive poly(methacrylic acid-co-acrylic acid)-co-polyvinylpyrrolidone magnetic nano-carrier for controlled delivery of fluvastatin.

A novel pH-responsive polymer, poly(methacrylic acid-co-acrylic acid)-co-polyvinyl-pyrrolidone (polymeric nano-carrier) was synthesized and used for encapsulation of 3-aminopropyl triethoxysilane modified Fe3O4 nanoparticles to prepare a new magnetic nano-carrier. The loading and release characteristics of both polymeric and magnetic nano-carriers were investigated using fluvastatin as the model drug. The loading behavior of the carriers was studied by varying concentration of fluvastatin in aqueous medium at 25°C and their release was followed spectrophotometrically (at 304 nm) at 37°C in three different solutions (buffered at pH1.2, 5.5 and 7.2) to simulate gastric and intestine medium. The effect of different parameters on the release of fluvastatin such as the amount of methacrylic acid monomer, cross-linker amount, initiator amount, and magnetic nanoparticles content was also studied. Considering the release kinetics and mechanism of the magnetic nanocarrier besides swelling behavior study of the polymeric nano-carrier reveal Fickian pattern and diffusion controlled mechanism for delivery of fluvastatin.

A novel optical DNA biosensor for detection of trace amounts of mercuric ions using gold nanoparticles introduced onto modified glass surface.

In this work we report a DNA spectrophotometric biosensor for detection of Hg2+ ions in which a pair of oligonucleotides with four thymine-thymine (T-T) mismatched bases was immobilized onto modified glass surface. Firstly, glass surface modified with 3-(mercaptopropyl) trimethoxysilane (MSPT) and gold nano-particles respectively and then one oligonucleotide (P1) modified with hexanthiol at 5-terminal was immobilized on gold nano-particles via self-assembly and inserted in methylene blue. Methylene blue can intercalate on single strand DNA (ss-DNA) and its absorption peak can measure spectrophotometrically. Then the other oligonucleotide was able to hybridize with P1 by forming thymine-Hg2+-thymine (T-Hg2+-T) complexes in the presence of Hg2+, and absorption signal of methylene blue reduced upon Hg2+ increasing concentration because inaccessibility of guanine base in DNA duplex. However, when Hg2+ was absent, the two oligonucleotides could not hybridize due to the T-T mismatched bases, and P2 could not be fixed on the modified glass surface and any change in absorption peak of methylene blue takes place. The UV-Vis spectrum showed a linear correlation between the absorption peak of methylene blue and the concentration of Hg2+ over the range from 10 nM to 10 µM (R2=0.9985) with a detection limit of 6 nM. This spectrophotometric biosensor could be widely used for selective detection of Hg2+.

Solid phase extraction of trace amounts of silver, cadmium, copper, mercury, and lead in various food samples based on ethylene glycol bis-mercaptoacetate modified 3-(trimethoxysilyl)-1-propanethiol coated Fe3O4 nanoparticles.

Extraction, pre-concentration, and determination of trace amounts of silver, cadmium, copper, mercury, and lead from some food samples were investigated by magnetic solid phase extraction using Fe3O4 nanoparticles coated with 3-(trimethoxysilyl)-1-propanethiol and modified with ethylene glycol bis-mercaptoacetate as a new adsorbent. SEM, X-ray diffraction, and FT-IR were used to characterise the adsorbent. Metal ions were measured using ICP-OES, except for mercury, which was determined by CV-AAS method. Various factors affecting the extraction and desorption of target metal ions were investigated. 1 mL of 1 mol/L HCl and 5% thiourea was used as eluent. The detection limits of 0.07, 0.06, 0.09, 0.01, and 0.08 ng/mL were obtained for silver, cadmium, copper, mercury, and lead with enrichment factors of 240, 294, 297, 291, and 236, respectively. The method was used for determination of target metal ions in rice, canned tuna fish, and tea leaves.

Magnetic nanoparticles solid phase extraction for determination of ochratoxin A in cereals using high-performance liquid chromatography with fluorescence detection.

A new, simple, fast, and environmental friendly sample preconcentration technique based on the modified Fe3O4 nanoparticles has been developed for extraction, and determination of ochratoxin A (OTA). Magnetic nanoparticles were coated with 3-(trimethoxysilyl)-1-propanethiol and modified by ethylene glycol bis-mercaptoacetate. Transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectrometry were used to characterize the adsorbents and the main parameters affecting the extraction and desorption efficiencies, such as pH of sample solution, sample volume, desorption conditions, extraction and desorption times, salt addition, and co-existing interferences have been investigated and established. Under optimal conditions, OTA was extracted and analyzed using high performance liquid chromatography with fluorescence detection. The mobile phase consists of acetonitrile:water:acetic acid (99:99:2, v/v/v) and fluorescence detection was performed with excitation and emission wavelengths at 333 and 477nm, respectively. An enrichment factor of 24 was achieved for OTA with relative standard deviation of <7%. The proposed method was applied to twenty samples of cereals (rice, wheat, and corn). The limits of detection of 0.06, 0.03, and 0.05ngmL(-1) and limits of quantitation of 0.19, 0.11, and 0.15ngmL(-1), were found for rice, wheat, and corn samples, respectively. The recoveries of OTA for spiked samples were ranged from 87 to 93%.

A new methodology for electrostatic immobilization of a non-labeled single strand DNA onto a self-assembled diazonium modified gold electrode and detection of its hybridization by differential pulse voltammetry.

In this work, a self-assembled diazonium modified gold electrode (D-MGE) was used for the fabrication of an electrochemical DNA biosensor. For preparation of D-MGE, initially 2-amino-5-mercapto-1, 3, 4-thiadiazole (AMT) self-assembled on gold electrode and a simple diazonation reaction was used to prepare D-MGE. Then, non-labeled single strand DNA (NL-ssDNA) directly was immobilized on D-MGE through electrostatic interaction. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) characterized the DNA biosensor fabrication process with the use of ferro-ferric cyanide as an electrochemical redox indicator. The hybridization capacity of the developed biosensor was monitored with differential pulse voltammetry using [Fe (CN)(6)](4-) as an indicating probe. A wide dynamic detection range (7.9 × 10(-11)-1.2 × 10(-7) mol L(-1)) and a low detection limit (1.4 × 10(-11) mol L(-1)) were achieved for the complementary sequence. In addition, the hybridization specificity experiments showed that the sensing system could accurately discriminate complementary sequence from non-complementary sequences.

Solid phase extraction of trace amounts of Ag, Cd, Cu, and Zn in environmental samples using magnetic nanoparticles coated by 3-(trimethoxysilyl)-1-propantiol and modified with 2-amino-5-mercapto-1,3,4-thiadiazole and their determination by ICP-OES.

A fast, sensitive, and simple method using magnetic nanoparticles (MNPs) coated by 3-(trimethoxysilyl)-1-propantiol and modified with 2-amino-5-mercapto-1,3,4-thiadiazole, as an adsorbent has been successfully developed for extraction, preconcentration, and determination of trace amounts of Ag, Cd, Cu, and Zn from environmental samples. The prepared nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). These magnetic nanoparticles can be easily dispersed in aqueous samples and retrieved by the application of external magnetic field via a piece of permanent magnet. The main factors affecting the extraction efficiency such as pH value, sample volume, eluent concentration and volume, ultrasonication time, and coexisting ions have been investigated and established. Under the optimal conditions, high concentration factors (194, 190, 170, and 182) were achieved for Ag, Cd, Cu, and Zn with relative standard deviations of 5.31%, 4.03%, 3.62%, and 4.20%, respectively. The limits of detection for Ag, Cd, Cu, and Zn were as low as 0.12, 0.12, 0.13 and 0.11 ng mL(-1). The prepared sorbent was applied for preconcentration of trace amounts of Ag, Cd, Cu, and Zn in the various water samples with satisfactory results.

Used gold nano-particles as an on/off switch for response of a potentiometric sensor to Al(III) or Cu(II) metal ions.

The potentiometric response of a carbon paste electrode modified with silica sol-gel and mercaptosuccinic acid (MSA) in the presence and absence of gold nano-particles was studied. The results showed that the electrode with gold nano-particles was responded to Al(3+) ions as a hard metal ion. On the other hand, the electrode without gold nano-particles was responded to copper ions as a soft metal ion. The electrodes without and with gold nano-particles exhibits a Nernstian slope of 29.1 and 19.2 mV decade(-1) for copper and aluminum ions over a wide concentration range of 4.3×10(-7)-1.0×10(-2) and 4.5×10(-7)-1.6×10(-3) mol L(-1), respectively. The detection limits of electrodes were 4.0×10(-7) and 1.6×10(-7) mol L(-1) for copper and aluminum ions, respectively.

Comparative studies of mercapto thiadiazoles self-assembled on gold nanoparticle as ionophores for Cu(II) carbon paste sensors.

Comparative studies of the potentiometric behavior of three mercapto compounds [2-((5-mercapto-1,3,4-thiadiazol-2-ylimino)methyl)phenol] (MTMP), [5-(2-methoxy benzylidene amino)-1,3,4-thiadiazole-2-thiol] (MBYT) and [5-(pyridin-2-ylmethyleneamino)-1,3,4-thiadiazole-2-thiol] (PYTT) self-assembled on gold nanoparticles (GNPs) as ionophores in carbon paste electrodes (CPEs) have been made. These mercapto thiadiazole compounds were self-assembled onto gold nanoparticles and then incorporated within carbon paste electrode. The self-assembled ionophores exhibit a high selectivity for copper ion (Cu(2+)), in which the sulfur and nitrogen atoms in their structure play a role as the effective coordination donor site for the copper ion. These carbon paste electrodes were applied as indicator electrodes for potentiometric determination of copper ions. The sensor based on PYTT exhibits the working concentration range of 4.0 x 10(-9) to 7.0 x 10(-2) M and a Nernstian slope of 28.7+/-0.3 mV decade(-1) of copper activity. The detection limit of electrode was 1.0 x 10(-9) M and potential response was pH independent across the range of 3.0-6.5. It exhibited a quick response time of <5 s and could be used for a period of 45 days. The ion selectivity of this electrode for Cu(2+) was over 10(4) times that for other metal cations. The application of prepared sensors has been demonstrated for the determination of copper ions in spiked water and natural water samples.

Chemometrics-assisted kinetic-potentiometric methods for simultaneous determination of Fe(II), Al(III), and Zr(IV) using a fluoride ion-selective electrode.

Partial least-squares (PLS) and principal component regression (PCR) were used for the simple, accurate, and simultaneous determination of Fe(III), Al(III), and Zr(IV) using the kinetic data from a novel potentiometric method. The complex forming reaction rate of Fe(III), Al(III), and Zr(IV) with fluoride ions was monitored by a fluoride ion-selective electrode. The experimental data showed the good ability of ion-selective electrodes as detectors, not only for the direct determination of fluoride ion, but also for simultaneous kinetic-potentiometric analysis using the PLS and PCR methods. The methods are based on the differences observed in the complexation rate of fluoride ions. Results have demonstrated that the simultaneous determination of Fe(III), Al(III), and Zr(IV) can be performed in concentration ranges of 0.5-18.5, 0.2-14.0, and 0.4-21.0 microg/mL, respectively. After the application of PLS, the total root mean square error of prediction (RMSEP) was found to be 0.121, 0.122, and 0.129 for the 10-sample experiment of Fe(III), Al(III), and Zr(IV), respectively. For PCR, the RMSEP was found to be 0.156, 0.162, and 0.178 for the 10-sample experiment of Fe(III), Al(III), and Zr(IV), respectively. The effects of certain foreign ions upon the reaction rate were determined for assessing the selectivity of the method. The proposed methods (H-point standard addition, PLS, and PCR) were evaluated using a set of synthetic sample mixtures, and applied for the simultaneous determination of Fe(III), Al(III), and Zr(IV) in water samples.

Voltammetric determination of some anti-malarial drugs using a carbon paste electrode modified with Cu(OH)2 nano-wire.

A sensitive electroanalytical methodology for the determination of chloroquine and primaquine using differential pulse voltammetry (DPV) at a Cu(OH)2 nano-wire-modified carbon paste electrode is presented. The cyclic voltammetric and DPV pulse voltammetric techniques are compared. The effects of scan rate and pH on current were investigated and an optimal scan rate of 50 mV s(-1) and a pH 5.5, 0.1 mol L(-1) phosphate buffer solution (PBS), were used. Additions of chloroquine and primaquine using DPV show linear ranges from 0.068 to 6.88 microg mL(-1) with a detection limit of 0.01 microg mL(-1) for chloroquine and 0.58-5.89 microg mL(-1) with a detection limit of 0.25 microg mL(-1) for primaquine. The method was then successfully utilized for the determination of chloroquine and primaquine in a real sample of their tablets and a recovery of 95% was obtained without interference from tablet matrix.

Copper(II) modified carbon paste electrodes based on self-assembled mercapto compounds-gold-nanoparticle.

Three mercapto compounds [2-mercapto-5-(1-methyl-5-nitroimidazole-2-yl)-1,3,4-thiadiazole] (MMNIT), [2-mercapto-5-(5-nitrofuran-2-yl)-1,3,4-thiadiazole] (MNFT) and [2-mercapto-5-(5-nitrothiophen-2-yl)-1,3,4-thidiazole] (MNTT) were used for self-assembled-gold nanoparticle (SAGNP) modified carbon paste electrodes. The electrodes were applied as indicator electrodes for potentiometric determination of Cu(II) ion. The prepared electrodes exhibit a Nernstian slope of 31.0+/-0.5 mV per decade for Cu(II) ion over a wide concentration range of 7.9x10(-9)-3.2x10(-2), 7.9x10(-9)-7.9x10(-4), and 2.8x10(-8)-7.9x10(-3) mol L(-1) for MMNIT, MNFT and, MNTT, respectively. The detection limits of electrodes were 3.5 (+/-0.2)x10(-9), 4.1x10(-9), and 4.1x10(-8) mol L(-1) of copper ion, respectively. The potentiometric responses of electrodes based on MMNIT, MNFT, and MNTT are independent of the pH of test solution in the pH range 2.0-5.5, 2.5-7.0, and 2.0-6.5, respectively. They have quick response with response time of about 5 s. The proposed electrodes show fairly good selectivity over some alkali, alkaline earth, transition and heavy metal ions. Finally, the proposed electrodes were successfully employed to detect Cu(II) ion in hair and water samples.

A novel Mn(2+) PVC membrane electrode based on a recently synthesized Schiff base.

A new PVC membrane electrode for manganese(II) ion based on a recently synthesized Schiff base of 5-[(4-nitrophenylazo)-N-hexylamine]salicylaldimine is reported. The electrode exhibits a Nernstian response for Mn(2+) ions over a wide concentration range (4.0x10(-7) to 1.8x10(-2)molL(-1)) with a slope of 30.1 (+/-1.0). The limit of detection is 1.0x10(-7)molL(-1). The electrode has a fast response time ( approximately 10s), a satisfactory reproducibility and relatively long life time. The proposed sensor revealed good selectivities over a wide variety of other cations include hard and soft metals. This electrode could be used in a pH range of 4.5-7.5. It was used as an indicator electrode in potentiometric titration of manganese(II) ions with EDTA solution.

A novel ion selective membrane potentiometric sensor for direct determination of Fe(III) in the presence of Fe(II).

A new PVC membrane potentiometric sensor that is highly selective to Fe(III) ions was prepared by using 2-[(2-hydroxy-1-propenyl-buta-1,3-dienylimino)-methyl]-4-p-tolylazo-phenol [HPDTP] as a suitable carrier. The electrode exhibits a linear response for iron(III) ions over a wide concentration range (3.5 x 10(-6) to 4.0 x 10(-2)) with a super Nernstian slope of 28.5 (+/-0.5) per decade. The electrode can be used in the pH range from 4.5 to 6.5. The proposed sensor shows fairly a good discriminating ability towards Fe(3+) ion in comparison to some hard and soft metals such as Fe(2+), Cd(2+), Cu(2+), Al(3+) and Ca(2+). It has a response time of <15s and can be used for at least 2 months without any measurable divergence in response characteristics. The electrode was used in the direct determination of Fe(3+) in aqueous samples and as an indicator electrode in potentiometric titration of Fe(III) ions.

Co2+-selective membrane electrode based on the Schiff Base NADS.

A new PVC membrane electrode for cobalt(II) ions based on a recently synthesized Schiff base of 5-((4-nitrophenyl)azo)- N-(2',4'-dimethoxyphenyl)salicylaldimine is reported. The electrode exhibits a Nernstian response for Co(2+) ions over a wide concentration range (9.0 x 10(-7)-1.0 x 10(-2) M) with a slope of 29(+/-1). The limit of detection is 8.0 x 10(-7) M. The proposed sensor revealed good selectivities over a wide variety of other cations including hard and soft metals. This electrode could be used in a pH range of 3.5-6.0. It was used as an indicator electrode in potentiometric titrations of cobalt(II) ions and can be used in the direct determination of Co(2+) in aqueous solutions.

Nickel(II) selective membrane potentiometric sensor using a recently synthesized mercapto compound as neutral carrier.

A PVC membrane electrode for Ni(2+) ions based on a recently synthesized mercapto compound, as an ionophore was prepared. The electrode exhibits a Nernstian slope of 28-30 mV per concentration decade at wide concentration range of (1.0x10(-2)-1.0x10(-7) M). It has a fast response time of <15 s and can be used for at least 4 weeks. The potentiometric response is independent of the pH of the test solution in the pH range 5-8.5. The proposed electrode revealed good selectivities over a wide variety of other cations including alkali, alkaline earth, transition and heavy metal ions. It was successfully applied to the direct determination and potentiometric titration of nickel ion with EDTA.