Preparation of silver hexacyanoferrate nanoparticles and its application for the simultaneous determination of ascorbic acid, dopamine and uric acid

A silver hexacyanoferrate nanoparticles/carbon nanotubes modified glassy carbon electrode was fabricated and then successfully used for the simultaneous determination of ascorbic acid, dopamine and uric acid by cyclic voltammetry. A detailed investigation by transmission electron microscopy (TEM) and electrochemistry was performed in order to elucidate the preparation process and properties of the nanocomposites. The size of silver hexacyanoferrate nanoparticles was examined by TEM around 27 nm. Linear calibration plots were obtained over the range of 4.0 × 10⁻⁶-7.8 × 10⁻⁵, 2.4 × 10⁻⁶-1.3 × 10⁻⁴ and 2.0 × 10⁻⁶-1.5 × 10⁻⁴ mol L⁻¹ with detection limits of 4.2 × 10⁻⁷,1.4 × 10⁻⁷ and 6.0 × 10⁻⁸ mol L⁻¹ for ascorbic acid, dopamine and uric acid, respectively. The practical analytical utilities of the modified electrode were demonstrated by the determination of ascorbic acid, dopamine and uric acid in urine and human blood serum samples.     

Flow-injection determination of hydrogen peroxide based on fluorescence quenching of chromotropic acid catalyzed with Fe(II)

Flow-injection analysis system (FIA system), which was based on Fe(II)-catalyzed oxidation of chromotropic acid with hydrogen peroxide, was developed for the determination of hydrogen peroxide. The chromotropic acid has a fluorescence measured at λ_em = 440 nm (emission wavelength) with λ_ex = 235 nm (excitation wavelength), and the fluorescence intensity at λ_em = 440 nm quietly decreased in the presence of hydrogen peroxide and Fe(II), which was caused by Fe(II)-catalyzed oxidation of chromotropic acid with hydrogen peroxide. By measuring the difference of fluorescence intensity, hydrogen peroxide (1.0 × 10⁻⁸-1.0 × 10⁻³ mol L⁻¹) could be determined by the proposed FIA system, whose analytical throughput was 40 samples h⁻¹. The relative standard deviation (RSD) was 1.03% (n = 10) for 4.0 × 10⁻⁸ mol L⁻¹ hydrogen peroxide. The proposed FIA technique could be applied to the determination of hydrogen peroxide in rain water samples.     

A novel fluorescence sensor based on covalent immobilization of 3-amino-9-ethylcarbazole by using silver nanoparticles as bridges and carriers

A novel technique of covalent immobilization of indicator dyes in the preparation of fluorescence sensors is developed. Silver nanoparticles are used as bridges and carriers for anchoring indicator dyes. 3-amino-9-ethylcarbazole (AEC) was employed as an example of indicator dyes with terminal amino groups and covalently immobilized onto the outmost surface of a quartz glass slide. First, the glass slide was functionalized by (3-mercaptopropyl) trimethoxysilane (MPS) to form a thiol-terminated self-assembled monolayer, where silver nanoparticles were strongly bound to the surface through covalent bonding. Then, 16-mercaptohexadecanoic acid (MHDA) was self-assembled to bring carboxylic groups onto the surface of silver nanoparticles. A further activation by using 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) converted the carboxylic groups into succinimide esters. Finally, the active succinimide esters on the surface of silver nanoparticles were reacted with AEC. Thus, AEC was covalently bound to the glass slide and an AEC-immobilized sensor was obtained. The sensor exhibited very satisfactory reproducibility and reversibility, rapid response and no dye-leaching. Rutin can quench the fluorescence intensity of the sensor and be measured by using the sensor. The linear response of the sensor to rutin covers the range from 2.0 × 10⁻⁶ to 1.5 × 10⁻⁴ mol L⁻¹ with a detection limit of 8.0 × 10⁻⁷ mol L⁻¹. The proposed technique may be feasible to the covalent immobilization of other dyes with primary amino groups.     

Rosmarinic acid determination using biomimetic sensor based on purple acid phosphatase mimetic

A new heterodinuclear Fe(III)Zn(II) complex which mimics the active site of the hydrolytic enzyme red kidney bean purple acid phosphatase was synthesized and characterized by IR, CHN and X-ray crystallographic analyses. This complex, [Fe^IIIZn^II(μ-OH)bpbpmp-CH₃](ClO₄)₂, containing the ligand (H₂bpbpmp-CH₃ = {2-[bis(2-pyridylmethyl)aminomethyl]-6-[(2-hydroxy-5-methylbenzyl) (2-pyridyl-methyl) aminomethyl]-4-methyl-phenol}) was employed in the construction of a biomimetic sensor and used in the determination of rosmarinic acid in plant extract samples. The response parameters and optimization of the biomimetic sensor design were evaluated. The best performance of this sensor was obtained for 75:15:10% (w/w/w) of the graphite powder:nujol:Fe(III)Zn(II) complex, 0.1 mol L⁻¹ phosphate buffer solution (pH 7.5), 1.19 × 10⁻⁴ mol L⁻¹ hydrogen peroxide with frequency, pulse amplitude, and scan increment at 30 Hz, 100 mV, and 0.6 mV, respectively. The rosmarinic acid concentration was linear in the range of 2.98 × 10⁻⁵ to 3.83 × 10⁻⁴ mol L⁻¹ (r = 0.9991) with a detection limit of 2.30 × 10⁻⁶ mol L⁻¹. This biomimetic sensor demonstrated long-term stability (300 days; 900 determinations) and reproducibility, with a relative standard deviation of 12.0%. The recovery study of rosmarinic acid in plant extract samples gave values from 90.3 to 98.3% and the concentrations determined showed agreement when compared with those obtained using capillary electrophoresis at the 95% confidence level.     

Study of the influence of silver nanoparticles on the second-order scattering and the fluorescence of the complexes of Tb(III) with quinolones and determination of the quinolones

Quinolones (Qs) can form the complex with Tb(III) ion, and the intramolecular energy transfer from Qs to Tb(III) takes place when excited. And thus the characteristic fluorescence of Tb(III) ion was enhanced and the maximum fluorescence peak locates at 545 nm. The second-order scattering (SOS) peak at 545 nm also appears for the Tb(III)-Qs complexes with the exciting wavelength of 274 nm. When the silver nanoparticles were added to the Tb(III)-Qs system, the luminescence intensity at 545 nm greatly increased. And the relative intensity is proportional to the amount of Qs. Based on this phenomenon, a novel method for determination of quinolones has been developed by using a common spectrofluorometer to measure the intensity of fluorescence and SOS. The luminescence intensity is greatly enhanced by silver nanoparticles in the pH range 5.5-6.2. The calibration graphs for pipemidic acid (PPA) and lomefloxacin (LMFX) are linear in the range 2.0 × 10⁻¹⁰ to 1.0 × 10⁻⁵ and 1.0 × 10⁻⁹ to 1.0 × 10⁻⁵ mol L⁻¹, respectively. The limits of detection are 4.7 × 10⁻¹¹ mol L⁻¹ for PPA and 1.1 × 10⁻¹⁰ mol L⁻¹ for LMFX. The method was applied satisfactorily to the determination of the two quinolones (Qs) in tablet, capsule, urine and serum samples. The experimental results showed that it is the certain size and certain concentration of silver nanoparticles that can greatly enhance the fluorescence -SOS intensity.     

An optical redox chemical sensor for determination of iodide

A novel optical sensor based on a redox reaction for the determination of iodide has been developed. The optode membrane is constructed by immobilization of methyltrioctylammonium chloride on triacetylcellulose polymer. The exchange of chloride as counter ion with iodate in the membrane changes the color to yellow, when it is placed in acidic solution of iodide. The sensor can readily be regenerated by 0.1 mol L⁻¹ NaOH in less than 15 s. The optode has a linear range of 3.94 × 10⁻⁶ to 5.51 × 10⁻⁵ mol L⁻¹ of iodide ions with a limit of detection 7.44 × 10⁻⁷ mol L⁻¹. The relative standard deviation for eight replicate measurements of 3.94 × 10⁻⁶ and 1.57 × 10⁻⁵ mol L⁻¹ of iodide was 2.83 and 1.38%, respectively. The sensor was successfully applied to the determination of iodide in tablet, powdered milk and urine samples.     

Biomimetic sensor based on MnMn complex as manganese peroxidase mimetic for determination of rutin

A novel biomimetic sensor for rutin determination based on a dinuclear complex [Mn^IIIMn^II(Ldtb)(μ-OAc)₂]BPh₄ containing an unsymmetrical dinucleating ligand, 2-[N,N-bis(2-pyridylmethyl)-aminomethyl]-6-[N-(3,5-di-tert-butyl-2-oxidoben-zyl)-N-(2-pyridylamino)aminomethyl]-4-methylphenol (H₂Ldtb), as a manganese peroxidase mimetic was developed. Several parameters were investigated to evaluate the performance of the biomimetic sensor obtained after the incorporation of the dinuclear complex in a carbon paste. The best performance was obtained in 75:15:10% (w/w/w) of the graphite powder:Nujol:Mn^IIIMn^II complex, 0.1 mol L⁻¹ phosphate buffer solution (pH 6.0) and 4.0 × 10⁻⁵ mol L⁻¹ hydrogen peroxide. The response of the sensor towards rutin concentration was linear using square wave voltammetry in the range of 9.99 × 10⁻⁷ to 6.54 × 10⁻⁵ mol L⁻¹ (r = 0.9998) with a detection limit of 1.75 × 10⁻⁷ mol L⁻¹. The recovery study performed with pharmaceuticals ranged from 96.6% to 103.2% and the relative standard deviation was 1.85% for a solution containing 1.0 × 10⁻³ mol L⁻¹ rutin (n = 6). The lifetime of this biomimetic sensor was 200 days (at least 750 determinations). The results obtained for rutin in pharmaceuticals using the biomimetic sensor and those obtained with the official method are in agreement at the 95% confidence level.     

FIA-near-infrared spectrofluorimetric trace determination of hydrogen peroxide using tricarchlorobocyanine dye (Cy.7.Cl) and horseradish peroxidase (HRP)

A new kind of near-infrared fluorescence agent, tricarbochlorocyanine dye (Cy.7.Cl), had been synthesized in house and used for near-infrared spectrofluorimetric determination of hydrogen peroxide (H₂O₂) by flow injection analysis (FIA) for the first time. The oxidation reaction of Cy.7.Cl with H₂O₂ occurred under the catalysis of horseradish peroxidase (HRP) and it was studied in detail. The possible reaction mechanism was discussed. Under optimal experimental conditions, fluorescence from Cy.7.Cl displayed excitation and emission maxima (ex/em) at 780 and 800 nm, respectively. The two linear working ranges were 1.86 × 10⁻⁷ to 4.11 × 10⁻⁷ mol L⁻¹ and 4.11 × 10⁻⁷ to 7.19 × 10⁻⁶ mol L⁻¹, respectively. The detection limit was 5.58 × 10⁻⁸ mol L⁻¹ of H₂O₂. The effect of interferences was studied. The proposed method was successfully applied to the determination of hydrogen peroxide in rainwater, serum and plant samples.     

Simultaneous voltammetric determination of paracetamol and caffeine in pharmaceutical formulations using a boron-doped diamond electrode

A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-doped diamond (BDD) electrode using square wave voltammetry (SWV) or differential pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 × 10⁻⁷ mol L⁻¹ to 8.3 × 10⁻⁵ mol L⁻¹ for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 × 10⁻⁷ mol L⁻¹ and 3.5 × 10⁻⁸ mol L⁻¹, respectively. The proposed method was successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level).     

Flow injection chemiluminescence sensor based on core–shell magnetic molecularly imprinted nanoparticles for determination of sulfadiazine

A novel flow injection chemiluminescence (FI-CL) sensor for determination of sulfadiazine (SDZ) using core–shell magnetic molecularly imprinted polymers (MMIPs) as recognition element is developed. Briefly, a hydrophilic MMIPs layer was produced at the surface of Fe₃O₄@SiO₂ magnetic nanoparticles (MNPs) via combination of molecular imprinting and reversible stimuli responsive hydrogel. And it provided the MMIPs with excellent adsorption capacity and rapid adsorption rate due to the imprinted sites mostly situated on the surface of MMIPs. Then the prepared SDZ-MMIPs were packed into flow cell to establish a novel FI-CL sensor. The sensor provided a wide linear range for SDZ of 4.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 1.54 × 10⁻⁷ mol L⁻¹. And the relative standard deviation (RSD) for the determination of 1.0 × 10⁻⁶ mol L⁻¹ SDZ was 2.56% (n = 11). The proposed method was applied to determine SDZ in urine samples and satisfactory results were obtained.     

Ultrasensitive determination of silver ion based on synchronous fluorescence spectroscopy with nanoparticles

Based on the characteristics of synchronous fluorescence spectroscopy (SFS), a new method with high sensitivity and selectivity was developed for rapid determination of silver ion with functional cadmium sulphide (CdS) nanoparticles as a fluorescence probe. When Δλ (λ_em − λ_ex) = 215 nm, maximum synchronous fluorescence is produced at 304 nm. Under optimal conditions, functional cadmium sulphide displayed a calibration response for silver ion over a wide concentration range from 0.8 × 10⁻¹⁰ to 1.5 × 10⁻⁸ mol L⁻¹. The limit of detection was 0.4 × 10⁻¹⁰ mol L⁻¹ and the relative standard deviation of seven replicate measurements for the lowest concentration (0.8 × 10⁻¹⁰ mol L⁻¹) was 2.8%. Compared with several fluorescence methods, the proposed method had a wider linear range and improved the sensitivity. Furthermore, the concentration dependence of the synchronous fluorescence intensity is effectively described by a Langmuir-type binding isotherm.     

Sensors based on galvanic cell generated electrochemiluminescence and its application

In this paper, a novel electrochemiluminescence (ECL) imaging sensor array was developed for determination of hydrogen peroxide (H₂O₂), which was based on Cu/Zn alloy galvanic cell generated ECL. In alkaline solution, Cu/Zn galvanic cell was formed because of corrosion effect, the galvanic cell could supply stable potential for ECL generation of luminol, and the weak ECL emission could be enhanced by H₂O₂. The galvanic cell sensor array was designed by putting Cu/Zn alloy in 96-well microtiter plates separately. The relative ECL intensity was proportional with the concentration of hydrogen peroxide in the range of 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol l⁻¹ and the detection limit was 3.0 × 10⁻⁷ mol l⁻¹ (3σ), the relative standard deviation (R.S.D.) for 11 parallel measurements of 1.0 × 10⁻⁵ mol l⁻¹ H₂O₂ was 4.0%.     

Molecularly imprinted conducting polymer based electrochemical sensor for detection of atrazine

An original electrochemical sensor based on molecularly imprinted conducting polymer (MICP) is developed, which enables the recognition of a small pesticide target molecule, atrazine. The conjugated MICP, poly(3,4-ethylenedioxythiophene-co-thiophene-acetic acid), has been electrochemically synthesized onto a platinum electrode following two steps: (i) polymerization of comonomers in the presence of atrazine, already associated to the acetic acid substituent through hydrogen bonding, and (ii) removal of atrazine from the resulting polymer, which leaves the acetic acid substituents open for association with atrazine. The obtained sensing MICP is highly specific towards newly added atrazine and the recognition can be quantitatively analyzed by the variation of the cyclic voltammogram of MICP. The developed sensor shows remarkable properties: selectivity towards triazinic family, large range of detection (10⁻⁹ mol L⁻¹ to 1.5 × 10⁻² mol L⁻¹ in atrazine) and low detection threshold (10⁻⁷ mol L⁻¹).     

Rapid simultaneous analysis of 1-hydroxypyrene, 2-hydroxyfluorene, 9-hydroxyphenanthrene, 1- and 2-naphthol in urine by first derivative synchronous fluorescence spectrometry using Tween-20 as a sensitizer

A novel method of first derivative synchronous fluorescence was developed for the rapid simultaneous analysis of trace 1-hydroxypyrene (1-OHP), 1-naphthol (1-NAP), 2-naphthol (2-NAP), 9-hydroxyphenanthrene (9-OHPe) and 2-hydroxyfluorene (2-OHFlu) in human urine. Only one single scan was needed for quantitative determination of five compounds simultaneously when Δλ = 10 nm was chosen. In the optimal experimental conditions, there was a linear relationship between the fluorescence intensity and the concentration of 1-OHP, 1-NAP, 2-NAP, 9-OHPe and 2-OHFlu in the range of 1.75 × 10⁻⁹ to 4.50 × 10⁻⁶ mol L⁻¹, 3.64 × 10⁻⁸ to 2.20 × 10⁻⁴ mol L⁻¹, 8.18 × 10⁻⁹ to 1.20 × 10⁻⁴ mol L⁻¹, 3.26 × 10⁻⁹ to 8.50 × 10⁻⁵ mol L⁻¹ and 4.88 × 10⁻⁹ to 5.50 × 10⁻⁶ mol L⁻¹, respectively. The limits of detection (LOD) were found to be 5.25 × 10⁻¹⁰ mol L⁻¹ for 1-OHP, 1.10 × 10⁻⁸ mol L⁻¹ for 1-NAP, 2.46 × 10⁻⁹ mol L⁻¹ for 2-NAP, 9.77 × 10⁻¹⁰ mol L⁻¹ for 9-OHPe and 1.46 × 10⁻⁹ mol L⁻¹ for 2-OHFlu. The proposed method is reliable, selective and sensitive, and has been used successfully in the determination of traces of 1-OHP, 1-NAP, 2-NAP, 9-OHPe and 2-OHFlu in human urine samples, whose results were in good agreement with those gained by the HPLC method.     

β−cyclodextrins-based inclusion complexes of CoFe2O4 magnetic nanoparticles as catalyst for the luminol chemiluminescence system and their applications in hydrogen peroxide detection

β−cyclodextrins (β−CD)-based inclusion complexes of CoFe₂O₄ magnetic nanoparticles (MNPs) were prepared and used as catalysts for chemiluminescence (CL) system using the luminol-hydrogen peroxide CL reaction as a model. The as-prepared inclusion complexes were characterized by XRD (X-ray diffraction), TGA (thermal gravimetric analysis) and FT-IR. The oxidation reaction between luminol and hydrogen peroxide in basic media initiated CL. The effect of β−CD-based inclusion complexes of CoFe₂O₄ magnetic nanoparticles and naked CoFe₂O₄ magnetic nanoparticles on the luminol-hydrogen peroxide CL system was investigated. It was found that inclusion complexes between β−CD and CoFe₂O₄ magnetic nanoparticles could greatly enhance the CL of the luminol-hydrogen peroxide system. Investigation on the kinetic curves and the chemiluminescence spectra of the luminol-hydrogen peroxide system demonstrates that addition of CoFe₂O₄ MNPs or inclusion complexes between β−CD and CoFe₂O₄ MNPs does not produce a new luminophor of the chemiluminescent reaction. The luminophor for the CL system was still the excited-state 3-aminophthalate anions (3-APA*). The enhanced CL signals were thus ascribed to the possible catalysis from CoFe₂O₄ MNPs or inclusion complexes between β−CD and CoFe₂O₄ nanoparticles. The feasibility of employing the proposed system for hydrogen peroxide sensing was also investigated. Experimental results showed that the CL emission intensity was linear with hydrogen peroxide concentration in the range of 1.0 × 10⁻⁷ to 4.0 × 10⁻⁶ mol L⁻¹ with a detection limit of 2.0 × 10⁻⁸ mol L⁻¹ under optimized conditions. The proposed method has been used to determine hydrogen peroxide in water samples successfully.     

The petentiometric determination of peroxide hydrogen and glucose on the glassy electrode modified by the calix[4]arene

A new petentiometric method to determine peroxide hydrogen and glucose had been studied. This method had been applied on the petentiometric determination of peroxide hydrogen and glucose in the total ionic strength adjustment buffer (TISAB) (pH 7.5) solution with the glassy electrode modified by the calix[4]arene. The glassy carbon electrode covered with the calix[4]arene depended on the H₂O₂ concentration in the range of log[H₂O₂] from −3.3 to −1.2 in the solution of TISAB (pH 7.5) with nearly Nernstian slope of about 65.6 ± 3 mV and the detection limit of peroxide hydrogen was 4.0 × 10⁻⁵ mol L⁻¹. The glassy carbon electrode covered with the calix[4]arene depended on the glucose concentration in the range of log[glucose] from −3.6 to −2.8 in the solution of TISAB (pH 7.5) with nearly Nernstian slope of about 50.2 ± 2 mV and the detection limit of glucose was 2.0 × 10⁻⁵ mol L⁻¹. The electrode had the good selectivity, sensitivity, stability and repeatability.     

An electrochemiluminescent biosensor for glucose based on the electrochemiluminescence of luminol on the nafion/glucose oxidase/poly(nickel(II)tetrasulfophthalocyanine)/multi-walled carbon nanotubes modified electrode

A poly(nickel(II) tetrasulfophthalocyanine)/multi-walled carbon nanotubes composite modified electrode (polyNiTSPc/MWNTs) was fabricated by electropolymerization of NiTSPc on MWNTs-modified glassy carbon electrode (GCE). The modified electrode was found to be able to greatly improve the emission of luminol electrochemiluminescence (ECL) in a solution containing hydrogen peroxide. Glucose oxidase (GOD) was immobilized on the surface of polyNiTSPc/MWNTs modified GC electrode by Nafion to establish an ECL glucose sensor. Under the optimum conditions, the linear response range of glucose was 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 8.0 × 10⁻⁸ mol L⁻¹ (defined as the concentration that could be detected at the signal-to-noise ratio of 3). The ECL sensor showed an outstanding well reproducibility and long-term stability. The established method has been applied to determine the glucose concentrations in real serum samples with satisfactory results.     

Determination of brominated phenols in water samples by on-line coupled isotachophoresis with capillary zone electrophoresis

A method for determination of nine brominated phenols as environmental risk compounds was developed by on-line coupled capillary isotachophoresis and capillary zone electrophoresis (ITP–CZE). For ITP step, 1 × 10⁻² mol L⁻¹ hydrochloric acid with 3 × 10⁻² mol L⁻¹ ammediol pH 9.1 was used as the leading electrolyte, and 3 × 10⁻² mol L⁻¹ β-alanine with 2 × 10⁻² mol L⁻¹ sodium hydroxide pH 10.05 was used as the terminating electrolyte. As the background electrolyte for CZE separation, 2.5 × 10⁻² mol L⁻¹ β-alanine with 2.5 × 10⁻² mol L⁻¹ lysine pH 9.6 was used. All electrolytes contained 0.05% or 0.1% (m/v) hydroxyethylcellulose to suppress the electroosmotic flow. UV detection at wavelength 220 nm was used. Detection limits in order of tens of nmol L⁻¹ were achieved. Good repeatability of migration times (less than 0.33% RSD) and good repeatability of peak areas (less than 7.19% RSD) at concentration level 5 × 10⁻⁸ mol L⁻¹ were observed. Developed ITP–CZE method was applied to determination of brominated phenols in spiked tap and river water samples.     

Simultaneous determination of N-acetyl-p-aminophenol and p-aminophenol with poly(3,4-ethylenedioxythiophene) modified glassy carbon electrode

A sensitive and selective method was developed for the determination of N-acetyl-p-aminophenol (APAP) and p-aminophenol (PAP) using poly(3,4-ethylenedioxythiophene) (PEDOT)-modified glassy carbon electrode (GCE). Cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical reaction of APAP and PAP at the modified electrode. Both APAP and PAP showed quasireversible redox reactions with formal potentials of 367 mV and 101 mV (vs. Ag/AgCl), respectively, in phosphate buffer solution of pH 7.0. The significant peak potential difference (266 mV) between APAP and PAP enabled the simultaneous determination both species based on differential pulse voltammetry. The voltammetric responses gave linear ranges of 1.0 × 10⁻⁶-1.0 × 10⁻⁴ mol L⁻¹ and 4.0 × 10⁻⁶-3.2 × 10⁻⁴ mol L⁻¹, with detection limits of 4.0 × 10⁻⁷ mol L⁻¹ and 1.2 × 10⁻⁶ mol L⁻¹ for APAP and PAP, respectively. The method was successfully applied for the determination of APAP and PAP in pharmaceutical formulations and biological samples.     

Biosensor for chlorogenic acid based on an ionic liquid containing iridium nanoparticles and polyphenol oxidase

A biosensor based on the ionic liquid, 1-n-butyl-3-methylimidazolium hexafluorophosphate containing dispersed iridium nanoparticles (Ir-BMI.PF₆) and polyphenol oxidase was constructed. This enzyme was obtained from the sugar apple (Annona squamosa), immobilized in chitosan ionically crosslinked with oxalate. The biosensor was used for determination of chlorogenic acid by square wave voltammetry. The polyphenol oxidase catalyzes the oxidation of chlorogenic acid to the corresponding o-quinone, which is electrochemically reduced back to this substance at +0.25 V vs. Ag/AgCl. Under optimized operational conditions the chlorogenic acid concentration was linear in the range of 3.48 × 10⁻⁶ to 4.95 × 10⁻⁵ mol L⁻¹ with a detection limit of 9.15 × 10⁻⁷ mol L⁻¹. The biosensor was applied in the determination of chlorogenic acid in organic and decaffeinated coffee and the results compared with those obtained using the capillary electrophoresis method. The recovery study for chlorogenic acid in these samples gave values of 93.2-105.7%.