Characterization and application of lornoxicam,europium(III), and lysozyme fluorescence

A novel and sensitive spectrofluorimetric method was developed for the determination of lornoxicam. The method was based on the fluorescence enhancement of europium(III) by formation of a ternary complex with lornoxicam in the presence of lysozyme as the co-ligand. The fluorescence signal for the lornoxicam-europium (III)-lysozyme system was monitored at an excitation wavelength of 620 nm and an emission wavelength of 390 nm. The parameters affecting the fluorescence intensity were optimized systematically and under these conditions the signal was directly proportional to the concentration of lornoxicam from 9.0 × 10^?5 to 1.0 × 10^?2 µg · mL^?1. The detection limit was 2.7 × 10^?5 µg · mL^?1. The relative standard deviation for thirteen replicate measurements of 1.0 × 10^?3 µg · mL^?1 lornoxicam was 1.8%. This method was employed for the determination of lornoxicam in pharmaceutical formulations and biological fluids. The mechanism of fluorescence for the lornoxicam-europium(III)-lysozyme system was discussed.     

CERIUM(IV)-BASED CHEMILUMINESCENCE OF FELODIPINE SENSITIZED BY RHODAMINE 6G

A simple, rapid, and sensitive flow injection chemiluminescence (FI-CL) method was proposed for the determination of felodipine. The method was based on the CL-emitting reaction between the studied drug and cerium(IV) in a nitric acid medium and measurement of the CL intensity produced by rhodamine 6G used as a sensitizer. Under the optimum conditions, the proposed procedure had a linear range between 5.0 × 10^?9 and 7.0 × 10^?6 g mL^?1, with a detection limit of 2.0 × 10^?9 g mL^?1. The relative standard deviation was 2.3% for 1.0 × 10^?7 g mL^?1 felodipine solution (n = 11). It was applied to the determination of felodipine in pharmaceutical preparations and biological fluids with satisfactory results. The possible mechanism of the chemiluminescence reaction was also discussed briefly.     

Flow Injection Chemiluminescence Analysis of Diphenhydramine Hydrochloride and Chlorpheniramine Maleate

Abstract

A new chemiluminescence (CL) method, using flow injection, is described for the determination of diphenhydramine hydrochloride and chlorpheniramine maleate. The method is based on the restraining effects on the CL reaction of luminol‐potassium ferricyanide in alkaline solutions. The various experimental parameters affecting the chemiluminescence intensity were studied carefully and incorporated into the procedure. The method allows the determination of 1.0–100 µg mL^?1 diphenhydramine hydrochloride and 0.1–10.0 µg mL^?1 chlorpheniramine maleate. The detection limits of the method are 0.3 µg mL^?1 for diphenhydramine hydrochloride and 0.02 µg mL^?1 for chlorpheniramine maleate. The method was successfully applied to the determination of diphenhydramine hydrochloride and chlorpheniramine maleate in pharmaceutical preparations.     

A PORTABLE FLOW INJECTION ANALYZER FOR THE IN SITU DETERMINATION OF FILTERABLE REACTIVE PHOSPHORUS (FRP) IN FRESHWATER

The development and deployment of a portable flow injection analyzer for continuous, real-time monitoring of filterable reactive phosphorus (FRP) in the Tamar catchment is described. The optimized method can be used for the determination of FRP in freshwater systems (4–150 μg L^?1 P) and is capable of sampling with high temporal resolution (up to 15 samples h^?1). The analyzer, fitted with a pre-filter and an in-line membrane filter (0.45 μm, cellulose acetate), was used in situ (bank-side and shipboard deployment) to provide real-time FRP data and in the laboratory to determine FRP in freshwater samples. The portable FRP analyzer was reproducible (RSD < 5%; n = 3) over the range 4–150 μg L^?1 P and accurate, achieving good agreement with a laboratory based air-segmented continuous flow analyzer reference method for a range of freshwater samples from the Tamar catchment in SW England.     

DETERMINATION OF PICOMOLE CONCENTRATIONS OF ALUMINUM (III) IN HUMAN SALIVA AND URINE BY A LUMINOL-CARBOXYMETHYL CHITOSAN CHEMILUMINESCENCE SYSTEM

A luminol–carboxymethyl chitosan (CMCS) system was established using flow injection chemiluminescence (CL) based on the enhancing effect of CMCS on the luminol–dissolved oxygen reaction. The CL intensity was linear with the CMCS concentration ranging from 0.01–30.0 µM. Al(III) was shown to quench the CL of the luminol–CMCS reaction, and the decrease of CL intensity was linear with the logarithm of Al(III) concentration over the range from 10–1000 pM with a detection limit of 3.5 pM (3σ). At a flow rate of 2.0 mL min^?1, the analysis was performed within 30 s. The proposed CL method was successfully applied to the determination of picomole levels Al(III) in human saliva and urine after oral intake of two aluminum hydroxide tablets, with recoveries from 90.6–108.7% and relative standard deviations <3% (n = 5). The results indicated that the excreted Al(III) in saliva and urine reached its maximum values at 3 hr and 2 hr, and the total excretive ratio were 1.24 × 10^?3% and 3.45% in 6 hr and 12 hr, respectively. The elimination rate constant k and the half–life time t _1/2 in human saliva and urine were 0.3747 hr^?1, 1.8495 hr, 0.7132 hr^?1, and 0.9717 hr, respectively. The possible CL mechanism of the luminol–CMCS–Al(III) reaction is discussed.     

Rapid and Sensitive Determination of Nucleic Acids by Enhanced Resonance Light Scattering Spectroscopy of Tetraphenyl Porphyrin Cobalt(II)Chloride

Abstract

A novel probe, tetraphenyl porphyrin Cobalt(II)chloride (CoTPPCl), was first developed for the determination of nucleic acids at a nanogram level by a resonance light scattering (RLS) technique. Under optimum conditions, the weak RLS signal of CoTPPCl was enhanced greatly by nucleic acids at 444.0 nm; the enhanced RLS intensity is proportional to the concentration of nucleic acids in the range of 0.05–3.5 mg L^?1 for calf thymus DNA and 0.03–4.2 mg L^?1 for fish sperm DNA. The detection limits (3δ) are 3.5 ng mL^?1 for calf thymus DNA and 4.5 ng mL^?1 for fish sperm DNA, respectively. The results show that determination of nucleic acids with CoTPPCl as a probe is much more sensitive than with α, β, γ, δ‐ tetrakis[4‐(trimethylammoniumyl)phenyl]porphine (TAPP). Synthetic samples and plasmid DNA extracted from K‐12‐HB101 colt were determined with satisfactory results.     

Rapid and Highly Sensitive Method for Protein Determination in Biological Samples with m‐Nitrophenylfluorone‐Mo(VI) Complex as a Spectral Probe

Abstract

A simple, rapid, highly sensitive, and selective method for detecting protein in biological samples has been developed, which is based on the interaction between protein and m‐nitrophenylfluorone‐Mo(VI) complex as a spectral probe. The optimum condition for the reaction is investigated. Bovine serum albumin (BSA) obeys Beer's law up to 10 µg · mL^?1, having a molar absorption coefficient of 8.51×10⁶ L · mol^?1 · cm^?1 at 535 nm. Many amino acids and metal ions do not interfere. The results of determination for biological samples are comparable to those obtained by the Bradford method. Meanwhile, the binding number is also determined.     

DESIGN OF A SENSITIVE MEMBRANE OPTODE FOR IRON DETERMINATION

An optical chemical sensor has been developed for the sensitive determination of Fe (III) ions by spectrophotometry. The optical membrane was constructed by immobilization of methyltrioctylammonium chloride on triacetylcellulose polymer. The exchange of thiocyanate as counter ion in the membrane sensitized this film to Fe (III). The sensing membrane is capable of determining Fe(III) reversibly over a dynamic range of 7.11 × 10^?7?8.88 × 10^?5 mol L^?1 with a limit of detection of 6.02 × 10^?7 mol L^?1 and a response time of 5 min. This optode can easily be regenerated by 0.1 mol L^?1 of sodium fluoride solution. The relative standard deviation for eight replicate measurements of 7.11 × 10^?6 and 5.33 × 10^?5 mol L^?1 of Fe (III) was 4.2 and 3.7%, respectively. The sensor was successfully applied for the determination of iron in tablet and water samples.     

Determination of baicalin in cosmetics and toothpaste by solid-phase extraction and high-performance liquid chromatography

Baicalin was determined in cosmetics and toothpaste by high-performance liquid chromatography. The samples were extracted with ultrasound in 75% ethanol for 20 min, purified by anion exchange solid-phase extraction cartridge, and the components were separated on a C18 column. The limits of detection and quantification were 3.0 mg kg^?1 and 10.0 mg kg^?1. The recovery was from 81.3–101.6%. A linear relationship was present from 1.00–100 µg · mL^?1 of baicalin. The protocol was simple, sensitive, selective, and used to determine baicalin in personal care products. Baicalin was not present in materials contrary to the labeled contents.     

Determination of copper in industrial water by innovative flow injection flame atomic absorption spectrometry

An online flow injection procedure for the preconcentration of copper at µg L^?1 levels was developed using a novel chelating resin and flame atomic absorption spectrometry for the analysis of industrial water. Amberlite XAD-2 functionalized with dithizone resin was packed in a minicolumn for flow injection. The pH, sample and eluent flow rates, and eluent concentration were optimized to ensure maximum recovery of Cu(II). The effect of concomittant ions on Cu (II) sorption was also investigated. The limit of detection and enrichment factor for a 180 s preconcentration time were 76 and 0.6 µg L^?1, respectively. The resin offered precision of 1.0% for seven successive determinations of 100 µg L^?1 Cu(II). The resin was used for more than 300 sorption and desorption cycles without appreciable loss of efficiency. The accuracy of the preconcentration procedure was confirmed by fortified recovery studies in industrial water with NIST certified copper nitrate with recovery exceeding 96%. Validation was performed by the analysis of a standard reference material.     

ON-LINE MINI-COLUMN SOLID-PHASE EXTRACTION COUPLED WITH SEQUENTIAL INJECTION FOR THE DETERMINATION OF CADMIUM IN ENVIRONMENTAL SAMPLES

□Trace cadmium(II) in environmental samples was separated and enriched in an automated fashion using a diphenylcarbazone-functionalized silica gel mini-column coupling with sequential injection. Cadmium was determined using a multicomponent system involving the analyte, potassium iodide, ethyl violet, and polyvinyl alcohol. Under the optimum conditions, the linear range for cadmium(II) was 0.015–0.50 µ g mL^?1, and the detection limit was 0.012 µ g mL^?1. The relative standard deviation of 11 determinations for 0.1 and 0.2 µ g mL^?1 standard solutions was smaller than 3.5%. This method was applied for the determination of cadmium(II) in water, plant, soil, and electroplating wastewater. No statistically significant differences in the results were observed between the reported method and those obtained by atomic absorption spectrometry. The analysis was performed within 13 min and a total reagent volume of only 0.14 mL (0.07 mL of eluent and 0.07 mL of reagents) was consumed in each determination of cadmium(II).     

On‐Line Preconcentration System for Cobalt Determination in Bee Honey Using Flow Injection‐Flame AAS

Abstract

A methodology for the on‐line preconcentration and determination of cobalt by flame atomic absorption spectrometry (FAAS) coupled with flow injection (FI) in bee honey samples is proposed. For the retention of cobalt, 2‐(5‐bromo‐2‐pyridylazo)‐5‐diethylaminophenol (5‐Br‐PADAP) complexing reagent, and Amberlite XAD‐7 resin were used, at pH 9.5. The Co‐(5‐Br‐PADAP) complexes were completely removed from the column with ethanol. An enrichment factor (EF) of 50‐fold for a sample volume of 50 mL was obtained. The detection limit (DL) for the preconcentration of 50 mL of aqueous solution was 0.18 µg L^?1. The precision for 10 replicate determinations at the 10 µg L^?1 cobalt levels was 3.6% relative standard deviation (RSD), calculated with peak heights obtained. The calibration graph using the preconcentration system for cobalt was linear with a correlation coefficient of 0.9997 at levels near the DL, up to at least 300 µg L^?1. The method was successfully applied to determination of total cobalt in honey samples.     

A Chitosan-Graphene Electrochemical Sensor for the Determination of Copper(II)

Graphite oxide was prepared by oxidizing graphite powder, reduced to graphene using hydrazine hydrate, and the grapheme was mixed with chitosan to form a composite that was used to modify a glassy carbon electrode for the determination of copper(II). The electrochemical behavior of the modified electrode was studied by cyclic and square wave voltammetries. The morphology and structure of the composite were characterized by infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. In addition, the proportion of composite material, pH, and adsorption time was optimized. Under the optimized experimental conditions, the sensor showed a linear dynamic range from 1.0 × 10^?9 to 1.5 × 10^?8 mol · L^?1 for copper(II) with a limit of detection of 4.3 × 10^?10 mol · L^?1 at a signal-to-noise ratio of three. The sensor displayed excellent electrochemical response and high sensitivity.     

DETERMINATION AND SEPARATION MECHANISM OF ACRYLAMIDE BY HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY

High-performance liquid chromatography using the negative peak method was developed for the determination and separation of acrylamide in food with methanol-water containing a background reagent of 0.01 mmol L^?1 5-sulfosalicylic acid (15/85, v/v) as the mobile phase with an ultraviolet-visible detector (λ_sig = 320 nm, λ_ref = 210 nm). The method was simple, the correlation coefficients exceeded 0.9990, and the limit of detection for acrylamide was 0.07 μg kg^?1. The concentrations of acrylamide in food were between 81 and 910 μg kg^?1. The recoveries were greater than 81.0% and the relative standard deviation was between 0.24 and 3.6%. The results showed that this method was suitable for the determination of acrylamide in food.     

DETERMINATION OF LEAD(II) BY FLOW-INJECTION ANALYSIS USING LUMINOL-POTASSIUM PERIODATE POST-CHEMILUMINESCENCE REACTION

The post-chemiluminescence (PCL) phenomenon arising from the potassium periodate–luminol reaction induced by lead(II) was investigated. A strong PCL signal was observed when lead(II) was injected into the mixture of potassium periodate and luminol in a flow-cell. The influencing factors on the PCL intensity of the system were investigated. Under the optimum experimental conditions, the present method allowed the determination of lead(II) in the concentration range of 1.0 × 10^?8 to 1.0 × 10^?5 mol/L and the detection limit for lead(II) was 2.3 × 10^?10 mol/L. The relative standard deviation was 3.2% for 11 replicate analyses of 1.0 × 10^?6 mol/L lead(II). Combined with cotton cellulose xanthate for separation, the proposed method was applied to the determination of lead(II) in real water samples with satisfactory results.     

Resonance Rayleigh Scattering of K2Zn3[Fe(CN)6]2 Nanoparticles and its Application for the Determination of Vitamin C

Abstract

In Britton-Robinson buffer medium, (pH 4.43), potassium ferricyanide (K₃[Fe(CN)₆]) could react with vitamin C (VC) to produce potassium ferrocyanide (K₄[Fe(CN)₆]), which further reacted with Zn²⁺ to form potassium zinc hexacyanoferate K₂Zn₃[Fe(CN)₆]₂ nanoparticles. The shapes and diameters of the K₂Zn₃[Fe(CN)₆]₂ nanoparticles have been observed with transmission electron microscopy, which showed the shapes of these nanoparticles was cubic and their average sizes were about 50 nm in the presence of 2.0 × 10^?5 mol L^?1 VC. The characteristics of resonance Rayleigh scattering (RRS) spectra of this reaction have been studied. The optimum reaction condition for the determination of VC has been investigated. It was found that the RRS intensity of the system at the RRS peak of 363.4 nm was proportional to the VC concentration in the range of 4.0?80.0 µmol L^?1, and the detection limit (3σ) for VC was 0.075 µmol L^?1. A novel and simple RRS method for the determination of VC based on the formation of K₂Zn₃[Fe(CN)₆]₂ nanoparticles has been established.     

A HYDROGEN PEROXIDE SENSOR BASED ON PRUSSIAN BLUE AND DNA-MODIFIED ELECTRODE

The polyvinylpyrrolidone (PVP) protected Prussian blue (PB) nanoparticles were prepared for use as a sensor for the catalytic reduction of hydrogen peroxide. The nanoparticles were used to modify a gold electrode, which was applied to detect hydrogen peroxide. Impedance spectra and differential pulse voltammetry were applied to detect the performance of the novel electrode and its response to H₂O₂ and Ramos cell smash fluid. Under the optimized experimental conditions, hydrogen peroxide was detected in a linear range of 6.25 × 10^?7 to 1.0 × 10^?5 mol · L^?1, and the detection limit was 7.12 × 10^?8 mol · L^?1 according to 3σ rule. Under the same conditions, hydrogen peroxide was determined in Ramos cell smash fluid with a linear range from 400–80000 mol mL^?1, with a detection limit of 114 mL^?1 according to 3σ rule. The modified electrode with Prussian blue nanoparticles displayed high sensitivity, good reproducibility, and long-term stability to hydrogen peroxide.     

Determination of Ammonia in Seawater by Multichannel Flow Injection Analysis

An analytical method that uses multichannel flow injection is reported to determine ammonia in seawater. The sample throughput was twenty-eight samples per hour. The linear dynamic range for ammonia was from 20.0–1000.0 μg N · L^?1 with a limit of detection of 0.27 μg N · L^?1, and recovery values between 98.1% and 104.6%. The relative standard deviation values for nitrogen as ammonia were 2.15–3.33% (n = 6). Statistical t-test analysis indicated that analysis by the flow injection method provided results that were statistically the same as standard procedures. The reported method was suitable for the determination of ammonia in seawater.     

STUDY ON THE INCLUSION INTERACTION BETWEEN SULFOBUTYLETHER-β-CYCLODEXTRIN AND CLOZAPINE BY FLOW INJECTION CHEMILUMINESCENCE

The inclusion interaction of sulfobutylether-β-cyclodextrin with clozapine was studied using flow injection chemiluminescence and molecular docking. By use of a homemade flow injection chemiluminescence model of lg[(I ₀?I _s)/I _s] = lgK + nlg[C _clozapine], the formation constant K, the stoichiometric ratio n, and thermodynamic parameters between sulfobutylether-β-cyclodextrin and clozapine were obtained. Results showed that the inclusion forming process of sulfobutylether-β-cyclodextrin/clozapine with a stoichiometric ratio of 1:1 was spontaneous through hydrophobic interaction. The molecular docking results showed that clozapine entered into the cavity of sulfobutylether-β-cyclodextrin with one hydrogen bond. Based on the good linear relationship of quenching of chemiluminescence intensity versus the logarithm of concentration between 0.07 and 50.0 ng mL^?1, a flow injection chemiluminescence method for clozapine was established for the first time with a detection limit of 0.02 ng mL^?1 (3σ). The proposed method was successfully applied for the determination of clozapine in spiked human urine and serum samples, with recoveries from 92.1–108.2% and relative standard deviations less than 2.7%.     

Determination of Lead in Spiked Seawater Samples by Electrothermal Atomic Absorption Spectrometry using Chemical Modifiers

Abstract

The determination of lead in spiked sodium chloride solution with 3.4% salinity and natural sea‐water samples by electrothermal atomic absorption spectrometry (ETAAS) with Zeeman‐effect background correction was investigated using neodymium, samarium, and erbium salts as modifiers with the addition of citric acid (CA) as a reducing agent. In order to demonstrate the high potential of rare earth metals in combination with citric acid, optimum pyrolysis temperature, atomization temperature, and optimum masses of neodymium, samarium, and erbium were found for the determination of lead. These modifiers were used for the determination of lead in sodium chloride solution with 3.4% salinity and in natural sea water samples by means of the calibration graphs prepared with pure analyte solutions.

The detection limits for lead spiked sample matrices were calculated with the 2σ criterion between 2.0 to 2.1 ng mL^?1 for neodymium and citric acid, between 5.3 to 7.4 ng mL^?1 for samarium and citric acid, and between 1.7 to 2.1 ng mL^?1 for erbium and citric acid and for a sample volume of 10 µL. The recoveries for lead spiked sea water samples were 97–102%, with neodymium and citric acid modifier and erbium and citric acid modifier. They were only 66–68% without modifier.