Vortex-Assisted Liquid–Liquid Microextraction for the Determination of Residual Sulfonamides in Meat Samples with Spectrofluorophotometer

A simple and fast extraction termed vortex-assisted liquid–liquid microrextraction coupled with molecular fluorescence spectroscopy has been developed and used for the detection of three sulfonamides (sulfadiazine sodium, sulfamethoxazole, and sulfaguanidine) in the meat samples. In the vortex-assisted liquid–liquid microrextraction method, 400 µL of nonanoic acid was used as extractant and directly injected into 10 mL centrifuge tube containing a derivative, which sulfonamides derived with o-phthaladehyde. And the extraction solvent was dispersed into the water phase under mechanical force with the vortex-mix. The polar side was reduced and the strong fluorescence produced at λ_ex = 295 nm. Variable parameters affecting the derivatization and vortex-assisted liquid–liquid microrextraction procedure were evaluated and optimized. The vortex-mix substituted effect of disperser solvent in this procedure. The limits of detection were 2.0 ng mL^?1 for sulfadiazine sodium and sulfamethoxazole, 0.5 ng mL^?1 for sulfaguanidine with the relative standard deviations of the method ranging from 2.5% to 6.1%. And the calibration graph was linear from 5 to 5000 ng mL^?1 with coefficient of determinations more than 0.9995. Recoveries of the three sulfonamides on spiked meat samples at different levels were 92.2–102.5%. Finally, the method has been successfully applied to the determination of sulfonamides from meat samples.     

A Validated Spectrofluorimetric Method for the Determination of Citalopram in Bulk and Pharmaceutical Preparations Based on the Measurement of the Silver Nanoparticles-Enhanced Fluorescence of Citalopram/Terbium Complexes

A simple, sensitive, and accurate spectrofluorimetric method was developed for the determination of citalopram in bulk and pharmaceutical preparations. The method is based on the enhancement of the weak fluorescence signal (FL) of the Tb (III)-citalopram system in the presence of silver nanoparticles. Fluorescence intensities were measured at 555 nm after excitation at 281 nm. Prepared silver nanoparticles (AgNPs) were characterized by UV-Visible spectra and transmission electron microscopy (TEM). Various factors affecting the formation of citalopram-Tb (III)-AgNPs complexes were studied and optimized. The fluorescence intensity versus concentration plot was linear over the range 0.02–14 μg?mL^?1, with an excellent correlation coefficient of 0.9978. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 7.15?×?10^?6?μg?mL^?1 and 2.38?×?10^?5?μg?mL^?1 respectively. The proposed method was found to have good reproducibility with a relative standard deviation of 3.66 % (n?=?6). The interference effects of common excipients found in pharmaceutical preparations were studied. The developed method was validated statistically by performing recoveries studies and successfully applied for the assay of citalopram in bulk powder and pharmaceutical preparations. Percent recoveries were found to range from 98.98 % to 100.97 % for bulk powder and from 96.57 % to 101.77 % for pharmaceutical preparations.     

Solid-Phase Extraction Using Polymer-Based Cartridge Modified with 2-(2-benzothiazolylazo)-3-hydroxyphenol for Preconcentration of Uranium(VI) Ions from Water and Real Samples

ABSTRACT

A highly sensitive, selective, and rapid method for the determination of ng mL^?1 level of U(VI) based on the rapid reaction of U(VI) with 2-(2-benzothiazolylazo)-3-hydroxyphenol (BTAHP) and the solid-phase extraction of the colored complex with a reversed-phase polymer-based C18 cartridge was developed. The BTAHP reacted with U(VI) to form a violet complex of molar ratio 2:1 [BTAHP to U(VI)] in the presence of 4.0 M of phosphoric acid solution and Triton X-114 medium. This complex was enriched by the solid-phase extraction with a polymer-based C18 cartridge. The enrichment factor of 200 was achieved. The molar absorptivity of the complex is 2.73 × 10⁶ L mol^?1 cm^?1 at 639 nm in the measured solution. The system obeys Beer's law in the range of 2.0–125 ng mL^?1, whereas the optimum concentration range obtained from Ringbom plot was 8.0–115 ng mL^?1. The relative standard deviation for 10-replicates sample of 100 ng mL^?1 level is 1.05%. The detection and quantification limits are 0.6 and 1.98 ng mL^?1 in the original sample. This method was applied to the determination of uranium(VI) in sea, tap, and waste waters, ore standard reference material, soil and sediment samples with good results comparing to the graphite furnace atomic absorption spectroscopy (GFAAS) method.     

Determination of Silver by Chemical Vapor Generation with In Situ Trapping Flame Atomic Absorption Spectrometry

ABSTRACT

The hyphenation of chemical vapor generation with an integrated atom trap system for flame atomic absorption spectrometry (CVG-IAT-FAAS) was evaluated for determination of silver in real samples (coal fly ash, sediment, and nickel alloy). The volatile species of silver were formed by reaction with sodium tetrahydroborate(III) in the presence of nitric acid. A new CVG-IAT-FAAS design (versus a water-cooled single silica tube, double-slotted quartz tube) significantly improved the sensitivity and detection limits compared with conventional flame atomic absorption spectrometry (FAAS) for determination of silver. The concentration limit of detection was 0.7 ng mL^?1 for Ag. The overall efficiency of the vapor generation process was estimated to be ca. 12%. For a 2 min in situ preconcentration time, sensitivity was enhanced 143-fold for Ag using the vapor generation atom trapping technique, compared to conventional FAAS. Sensitivity can be further improved by increasing the collection time. The precision of measurement at 10 ng mL^?1 of Ag was 10% RSD. The accuracy of this method was validated by analyses of NRC GBW 07302 (Stream Sediment), BCS CRM No. 346 (Nickel Alloy), NIST SRM 2710 (Montana Soil), NRCC LUTS-1 (Lobster Hepatopancreas), and NIST SRM 1643e (Trace Element in Water) certified reference materials. The measured Ag contents in these five reference materials were in satisfactory agreement with the certified values (spanning the range of 0.066–35 µg g^?1).     

Sensitive Chemiluminescence Assay for Patulin in Apple Juice by Flow Injection

Abstract

A sensitive chemiluminescence (CL) procedure for the determination of patulin by flow injection is described. It was found that patulin inhibits the CL generated from the luminol–dissolved oxygen system significantly. The decrement of chemiluminescence intensity was linear with the patulin concentration over the range from 0.04 to 10.0 ng mL^?1 with a detection limit of 0.01 ng mL^?1 (3σ_noise). At a flow rate of 2.0 mL min^?1, a complete analytical process could be performed within 0.5 min, including sampling and washing, with a relative standard deviation of less than 3.0% (n=5). The proposed method was applied successfully in the determination of patulin in apple juice, and the recovery was between 96.9% and 103.9%.     

Novel Method for Determination of Anthracene by Coupling Dispersive Liquid-Liquid Extraction to First-Derivative Synchronous Spectrofluorimetry

A novel method could be adopted successfully for determination of anthracene in environmental samples, utilizing dispersive liquid-liquid extraction followed by first-derivative synchronous fluorimetry at a constant wavelength difference Δλ?=?165 nm, where a linear calibration curve was obtained in a concentration range of 0.5–100 ng mL^?1 at 244 nm. The detection limit was 0.1 ng mL^?1. The method can be easily adopted for determination of anthracene in aqueous media including tap water and river water. The recoveries obtained were 85.40–108.02 %. The proposed method was validated according to International Conference of Harmonization (ICH) guide lines and successfully applied to determine anthracene in pure form and in water samples including real life water samples from different sources. All the results obtained were compared with those of published method, where no a significant difference was observed.     

UV–Vis Spectrophotometric Determination of Mercury Based on Room Temperature Ionic Liquids Enhanced Hollow-Fiber Liquid-Phase Microextraction

A novel method based on the enhancement effect of room temperature ionic liquids for hollow-fiber liquid-phase microextraction trace amounts of mercury combined with UV–Vis spectrophotometry for the determination of Hg was developed. The addition of room temperature ionic liquids led to 6.0 times improvement in the determination of mercury. Under optimized conditions, an enrichment factor of 120 could be obtained, and the detection limit for Hg was 0.2 ng mL^?1. The relative standard deviations for five replicate determinations of 20 ng mL^?1 Hg(II) was 5.4%. The proposed method was successfully applied to certified reference materials and environmental water samples with satisfactory results for the determination of Hg.     

Spectroscopic Study on the Interaction of Pyronine Y with Nucleic Acids and Its Analytical Application

ABSTRACT

The interaction of pyronine Y (PY) with nucleic acids was studied by resonance Rayleigh scattering (RRS) for nucleic acid detection. The enhanced RRS intensity of nucleic acids reacted with PY was proportional to the concentration of nucleic acids in the ranges of 27.0–625 ng ml^?1 for fish sperm DNA, 39.0–500 ng ml^?1 for calf thymus DNA, and 59.0–375 ng ml^?1 for yeast RNA. The limits of determination were 0.2 ng ml^?1 for fish sperm DNA, 0.6 ng ml^?1 for calf thymus DNA, and 0.7 ng ml^?1 for yeast RNA. The method had been successfully applied to the quick determination of nucleic acids in synthetic and natural samples.     

Comparative Study on Three Different Systems of Chemiluminescence Flow‐Injection Determination of Leucogen

Abstract

The effects of three systems on the chemiluminescence (CL) intensity have been studied in this paper, such as leucogen–potassium permanganate–rhodamine B, leucogen–cerium (IV)–rhodamine B, and leucogen–luminol–hydrogen peroxide (called system 1, system 2, and system 3, respectively). The mechanism of these reactions is also discussed. Surfactant (CTMAB) has a remarkably sensitive effect on these systems mentioned above. Therefore, three new flow injection chemiluminescence methods for the determination of leucogen have been established. For system 1, the linear range is 8.0×10^?8 to 4.0×10^?5 g mL^?1, with limits of detection 2×10^?8 g mL^?1; the relative standard deviation is 2.5% (n=11, Cs=4.0×10^?6 g mL^?1). For system 2, the linear range is 1.0×10^?8 to 5.0×10^?6 g mL^?1, with limits of detection 3×10^?9 g mL^?1; the relative standard deviation is 5.1% (n=11, Cs=1.0×10^?6 g mL^?1). For system 3, the linear range is 4.0×10^?8 to 2.0×10^?6 g mL^?1, with limits of detection 1×10^?8 g mL^?1; the relative standard deviation is 1.3% (n=11, Cs=1.0×10^?7 g mL^?1). Compared with the three methods above, system 3 is confirmed as the best method. This method has been applied to the determination of leucogen with satisfactory results.     

Multipumping Nitrite Determination in Exhaled Breath Condensate

Abstract

A flow system based on multicommutation is proposed for the rapid, clean, and inexpensive determination of nitrites in small volumes of breath condensates. The procedure exploits the colorimetric detection of nitrite with the Griess reagent [0.03% naphthylethylene diamine dihydrochloride (NED), 0.5% sulpfhanilamide, and 3.0% phosphoric acid] in acidic medium at 540 nm correcting the variations of the baseline with measurements at 424 nm. The flow system was designed with a set of solenoid micropumps to minimize sample and reagent consumption and waste generation. The detection limit was estimated as 3.8 ng mL^?1 (99.7% confidence level) with a linear response ranging up to 500 ng mL^?1. The coefficient of variation was estimated as 0.7% for a solution containing 300 ng mL^?1 nitrite (n=9). Approximately 144 determinations can be carried out per hour, consuming only 678.4 µg Griess reagent and generating 1.184 mL of effluent per determination, thus providing an environmentally friendly alternative and a nonexpensive method. The procedure was successfully applied to determine nitrite in breath condensates.     

Cloud-Point Extraction and Spectrophotometric Determination of Trace Quantities of Bismuth in Environmental Water and Biological Samples

ABSTRACT

A cloud-point extraction (CPE) process using the nonionic surfactant Triton X-114 to extract bismuth from aqueous solutions was investigated. The method is based on the complexation reaction of Bi(III) with 4-(2-benzothiazolylazo)2,2′-biphenyldiol (BTABD) and micelle-mediated extraction of the complex. The optimal extraction and reaction conditions (e.g., pH, reagent concentration, surfactant concentration, and effect of time) were studied. The analytical characteristics of the method (e.g., linear range, molar absorptivity, Sandell sensitivity, optimum Ringbom concentration ranges, limits of detection and quantification, preconcentration factor, and improvement factors) were obtained. Linearity was obeyed in the range of 2.50–85.0 ng mL^?1 of Bi(III) ion. The detection limit of the method was 0.75 ng mL^?1 of Bi(III) ion. The interference effect of some anions and cations was also tested. The method was applied to the determination of bismuth in environmental water, human hair, and urine samples.     

Sensitive Detection of Luteolin Using Thioglycolic Acid–Capped Cadmium Telluride/Cadmium Sulphide Quantum Dots as the Fluorescent Probe

ABSTRACT

A sensitive and simple method for the determination of luteolin (LTL) was developed based on the fluorescence quenching effect of LTL for thioglycolic acid–capped (TGA-capped) CdTe/CdS quantum dots (QDs). Under optimum conditions, a good linear relationship was obtained from 0.3 to 20.0 µg · mL^?1 with a correlation coefficient of 0.9972, and the detection limit was 7.2 ng · mL^?1. The fluorescence quenching mechanism has been proposed on the basis of electron transfer supported by ultraviolet-visible (UV-Vis) absorption, fluorescence (FL) spectroscopy. The proposed method was successfully applied to the determination of LTL in commercial capsules and human urine samples. It manifested several advantages such as high sensitivity, short analysis time, low cost, and ease of operation.     

Determination of Cd in Water Samples by Hollow-Fiber–Supported Liquid-Membrane Extraction Coupled with Thermospray-Flame–Furnace Atomic-Absorption Spectrometry

ABSTRACT

A new method of hollow-fiber–supported liquid-membrane extraction (HF-SLME) coupled with thermospray-flame–furnace atomic-absorption spectrometry (TS-FF-AAS) for the determination of cadmium in water samples was developed. 1-Octanol was immobilized in the pores of the polypropylene hollow fiber as liquid membrane and used as the acceptor solution. Cd was selectively extracted from water samples into 1-octanol that filled the inner part of hollow fiber as the acceptor solution. The authors evaluated in detail some parameters that influence extraction and determination, such as the concentration of sodium diethyldithiocarbamate (DDTC), pH of samples, stirring rate, extraction time, flow rate of the pump, and interferences. Under optimized conditions, an enrichment factor of 146 could be obtained. In combination with thermospray-flame–furnace atomic-absorption spectrometry, a very low limit of detection (LOD) (5 ng L^?1) was achieved. The relative standard deviation (RSD) was 4.3% for five determinations of 0.1 ng mL^?1 cadmium. The accuracy of this method was validated by determination of certified reference water samples (GBW(E) 08607 and GSBZ(E) 50009-88). The proposed method was also applied to the determination of cadmium in tap water and river water, with the recoveries in the range of 90–96% for spiked samples.     

A Sensitive Chemiluminescence Flow Injection Procedure for Assay of Fluoride in Waters and Humane Urine by Use of Immobilized Reagents

A new simple, rapid, selective and sensitive analytical procedure based on chemiluminescence (CL) detection is described for the determination of free fluoride at sub‐nanogram levels by use of controlled‐reagent‐release technology in a flow injection system. The analytical reagents involved in the CL reaction, including luminol and periodate, were both immobilized on anion‐exchange resins in a flow injection system. Through water injection luminol and periodate were eluted from the anion exchange column to generate the chemiluminescence, which was enhanced in the presence of fluoride. The increased CL intensity was linear with fluoride concentration in the range from 0.1 to 10 ng·mL^? 1. The limit of detection was 20 pg·mL^? 1 (3σ) and the relative standard deviation (RSD) was 1.02% (n = 5) for a 1.0 ng·mL^? 1 fluoride. At a flow rate of 2.0 mL·min^? 1, including sampling and washing, a typical analytical procedure could be performed in 0.5 min with a RSD of less than 3.0%. The proposed method was successfully applied to determine the free fluoride in water and human urine, and the results were in good agreement with those obtained by ion chromatography.     

Automated Flow Injection Method for Monitoring Total Cyanide Concentration in Petroleum Refinery Effluents Using Ninhydrin as Color Reagent

Abstract

An automated flow injection system was developed for monitoring cyanide concentration in effluents from petroleum refineries. The method takes advantage of the reaction of cyanide ions with ninhydrin in basic medium in a flow injection system. A linear range of 0.01 to 0.04 µg mL^?1 was obtained with a detection limit of 1.5 ng mL^?1 by using 500 µL sample injection, with an analytical throughput of 30 samples hr^?1, excluding sample pretreatment by distillation if required. Regarding interferences, cyanide can be determined in the presence of 100 mg L^?1 of thyocianate and sulfide, both species normally found in industrial effluents. For total cyanide determination, strong acid distillation is recommended due to the presence of cyano‐metallic complexes in the refinery effluents. The method was validated by analyte addition and results compared with the standard methodology proposed by the American Public Health Association (APHA). The more significant advantage of the proposed method is the lack of use of carcinogenic reagent such as pyridine and psychotropic compound such as barbituric acid, both used in the recommended method by APHA. Thus, the proposed method is really a friendly analytical procedure.     

The Mineral Content of Rhizona cyperi after Microwave-Assisted Digestion and Determination by AAS

ABSTRACT

Rhizoma cyperi (tuberal part of Cyperus rotundus Linn) obtained from 15 different zones of China was studied to determine the contents of 16 trace elements such as 4 minor (Ca, K, Mg, and Na), 9 trace (Co, Cr, Cu, Fe, Mn, Mo, Ni, V, and Zn), and 3 toxic (Ag, Cd, and Pb) elements. The concentration determination of 16 elements was performed by atomic absorption spectrophotometry (AAS) after microwave-assisted digestion. A microwave-assisted digestion procedure based on the mixture nitric acid–hydrogen peroxide was evaluated. The method was successfully validated with the good recoveries (97–105%) against CRM GBW07603 (bush twigs and leaves). The calibration curve furnished good linear correlation coefficients (r = 0.9956–0.9999), excellent recoveries (99.35–103.7%), and limits of detection (LOD = 1–50 ng·mL^?1) suitable to determine in Rhizoma cyperi. The results showed that K, Ca, Mg, and Na were the most abundant of the major elements in Rhizoma cyperi with average concentrations of K, 26,221 µg·g^?1; Ca, 1097 µg·g^?1; Mg, 714 µg·g^?1, and Na, 293 µg·g^?1, respectively. K element was determined for the first time in this plant.     

Flow‐Injection Chemiluminescence Study of Luminol–Hydrogen Peroxide–Carbendazim System

Abstract

A new flow‐injection chemiluminescence (CL) method is described for the determination of carbendazim. The method is based on the CL reaction of luminol and hydrogen peroxide (H₂O₂). Carbendazim can greatly enhance the chemiluminescence intensity in sodium hydroxide–sodium dihydrogen phosphate (NaOH–NaH₂PO₄) medium (pH=12.6). Under the optimum conditions, the linear range for the determination of carbendazim is 2.00×10^?8 to 2.00×10^?6 g mL^?1 with a detection limit (S/N=3) of 7.24×10^?9 g mL^?1. The relative standard deviation is 1.8% for 1.0×10^?7 g mL^?1 carbendazim (n=8). The proposed method has been applied to the determination of carbendazim in tap‐water samples. Furthermore, the possible enhanced CL mechanism is discussed by examining the CL spectra and fluorescence spectra.     

Selective Spectrofluorimetric Method with Enhanced Sensitivity for Determination of Silodosine in Dosage Form and Human Plasma. Application to Stability Studies and Content Uniformity Testing

A novel, sensitive and selective spectrofluorimetric method has been developed and validated for determination of silodosine (SLD) in its dosage form and human plasma. The method is based on nucleophilic substitution reaction of SLD with 5-(dimethylamino) naphthalene-1-sulfonyl chloride (dansyl chloride) in presence of 5.0 × 10^?4 M sodium carbonate (pH 10.50) to yield a highly fluorescent derivative that was measured at 435 nm after excitation at 347 nm. The different experimental parameters affecting the development and stability of the reaction product were carefully studied and optimized. The fluorescence-concentration plot was rectilinear over the range 30.0–200.0 ng ml^?1, with a correlation coefficient of 0.9979. The limits of detection (LOD) and quantification (LOQ) were found to be 5.44 and 16.47 ng ml^?1, respectively. The proposed method was validated according to ICH guidelines, and successfully applied to the assay of commercial capsules as well as content uniformity testing. The high sensitivity of the proposed method allowed its successful application to the analysis of SLD in spiked human plasma with % recovery of 92.88 ± 1.05–100.73 ± 0.75%, (n = 6). The application of the proposed method was further extended to stability studies of SLD after exposure to different forced degradation conditions, such as acidic, alkaline and oxidative conditions, according to ICH guidelines, where this work describe the first attempt for selective spectrofluorimetric determination of silodosine in plasma and in the presence of its oxidative degradation.     

Flow Injection Kinetic Spectrophotometric Determination of Cerium Based on the Decolorization Reaction Between Arsenazo III and Cerium (IV)

ABSTRACT

Trace amounts of cerium were analyzed by flow injection kinetic spectrophotometry, based on the decolorization reaction between arsenazo III and Ce(IV) in sulfuric acid medium at room temperature. The absorbance difference (ΔA) of decolorization was linear with the concentration of Ce(IV). The flow injection technique was used to precisely control the timing. Under the optimum conditions, the determination of Ce(IV) in the range 0.0–8.0 µg mL^?1 with a correlation coefficient (r) of 0.9982, the regression equation was ΔA = 0.0014 + 0.0406c (µg mL^?1). The detection limit (3σ) of 0.2 µg mL^?1 was achieved at a sampling frequency of 60 h^?1. The proposed method was applied to the analyses of Ce in soil successfully.