High extraction efficiency for polar aromatic compounds in natural water samples using multiwalled carbon nanotubes/Nafion solid-phase microextraction coating

A novel solid-phase microextraction (SPME) fiber coated with multiwalled carbon nanotubes (MWCNTs)/Nafion was developed and applied for the extraction of polar aromatic compounds (PACs) in natural water samples. The characteristics and the application of this fiber were investigated. Electron microscope photographs indicated that the MWCNTs/Nafion coating with average thickness of 12.5 μm was homogeneous and porous. The MWCNTs/Nafion coated fiber exhibited higher extraction efficiency towards polar aromatic compounds compared to an 85 μm commercial PA fiber. SPME experimental conditions, such as fiber coating, extraction time, stirring rate, desorption temperature and desorption time, were optimized in order to improve the extraction efficiency. The calibration curves were linear from 0.01 to 10 μg mL⁻¹ for five PACs studied except p-nitroaniline (from 0.005 to 10 μg mL⁻¹) and m-cresol (from 0.001 to 10 μg mL⁻¹), and detection limits were within the range of 0.03–0.57 ng mL⁻¹. Single fiber and fiber-to-fiber reproducibility were less than 7.5 (n = 7) and 10.0% (n = 5), respectively. The recovery of the PACs spiked in natural water samples at 1 μg mL⁻¹ ranged from 83.3 to 106.0%.     

Simultaneous determination of salbutamol sulphate, bromhexine hydrochloride and etofylline in pharmaceutical formulations with the use of four rapid derivative spectrophotometric methods

Four simple, rapid, accurate, precise, reliable and economical spectrophotometric methods have been proposed for simultaneous determination of salbutamol sulphate (SS), bromhexine hydrochloride (BH) and etofylline (ET) in pure and commercial formulations without any prior separation or purification. They were first derivative zero crossing spectrophotometry (method 1), simultaneous equation method (method 2), derivative ratio spectra zero crossing method (method 3) and double divisor ratio spectra derivative method (method 4). The ranges for SS, BH and ET were found to be 1-35 μg mL⁻¹, 4-40 μg mL⁻¹ and 5-80 μg mL⁻¹. For methods 1 and 2, the values of limit of detection (LOD) were 0.2314 μg mL⁻¹, 0.4865 μg mL⁻¹ and 0.2766 μg mL⁻¹ and the values of limit of quantitation (LOQ) were 0.7712 μg mL⁻¹, 1.6217 μg mL⁻¹ and 0.9221 μg mL⁻¹ for SS, BH and ET, respectively. For method 3, LOD values were 0.3297 μg mL⁻¹, 0.2784 μg mL⁻¹ and 0.7906 μg mL⁻¹ and LOQ values were 0.9325 μg mL⁻¹, 0.9282 μg mL⁻¹ and 2.6352 μg mL⁻¹ for SS, BH and ET, respectively. For method 4, LOD values were 0.3161 μg mL⁻¹, 0.2495 μg mL⁻¹ and 0.2064 μg mL⁻¹ and LOQ values were 0.9869 μg mL⁻¹, 0.8317 μg mL⁻¹ and 0.6879 μg mL⁻¹ for SS, BH and ET. The precision values were less then 2% R.S.D. for all four methods. The common excipients and additives did not interfere in their determinations. The results obtained by the proposed methods have been statistically compared by means of Student t-test and by the variance ratio F-test.     

Development of a validated liquid chromatographic method for the quality control of Prunellae Spica: Determination of triterpenic acids

A simple and rapid reversed-phase HPLC-UV method was developed for the determination of triterpenic acids in the crude extract of Prunellae Spica. Five triterpenic acids were extracted and isolated from P. Spica as marker compounds for use in the quality control of herbal medicines. Various solvent extraction techniques were evaluated, and the greatest efficiency was observed with sonication in 100% ethanol. Elemental compositions of the five marker compounds were determined by high-resolution mass spectroscopy. The dynamic range of the HPLC-UV method depended on the specific analyte, and acceptable quantitation was obtained between 10 and 250 μg mL⁻¹ for oleanolic acid, between 10 and 300 μg mL⁻¹ for ursolic acid, between 3 and 75 μg mL⁻¹ for 2α,3α,24-trihydroxyolean-12en-28oic acid, between 5 and 100 μg mL⁻¹ for euscaphic acid, and between 5 and 100 μg mL⁻¹ for 2α,3α-dihydroxyurs-12en-28oic acid. The method was deemed satisfactory by inter- and intra-day validation and exhibited both high accuracy and precision (relative standard deviation <9.4%). Overall limits of quantitation and detection were approximately 0.5-2.5 μg mL⁻¹ at a signal-to-noise ratio (S/N) of 3 and were about 3.0-10.0 μg mL⁻¹ at a S/N of 10. In addition, principal component analysis (PCA) was performed on the analytical data of 15 different P. Spica samples in order to classify samples collected from different regions.     

A rapid, acetonitrile-free, HPLC method for determination of melamine in infant formula

A simple, precise, accurate and validated, acetonitrile-free, reverse phase high performance liquid chromatography (HPLC) method is developed for the determination of melamine in dry and liquid infant formula. The separation is performed on a Kromasil C18 column (150 mm × 3.2 mm I.D., 5 μm particle size) at room temperature. The mobile phase (0.1% TFA/methanol 90:10) is pumped at a flow rate of 0.3 mL min⁻¹ with detection at 240 nm. Melamine elutes at 3.7 min. A linear response (r > 0.999) is observed for samples ranging from 1.0 to 80 μg mL⁻¹. The method provides recoveries of 97.2-101.2% in the concentration range of 5-40 μg mL⁻¹, intra- and inter-day variation in <1.0% R.S.D. The limit of detection (LOD) and limit of quantification (LOQ) values are 0.1 μg mL⁻¹ and 0.2 μg mL⁻¹, respectively.     

Ligandless-dispersive liquid-liquid microextraction of trace amount of copper ions

In the present work, a new ligandless-dispersive liquid-liquid microextraction (LL-DLLME) method has been developed for preconcentration trace amounts of copper as a prior step to its determination by flame atomic absorption spectrometry. In the proposed approach 1,2-dicholorobenzene and ethanol were used as extraction and dispersive solvents, respectively. Some factors influencing on the extraction efficiency of copper and its subsequent determination were studied and optimized, such as the extraction and dispersive solvent type and volume, pH of sample solution, extraction time and salting out effect. Under the optimal conditions, the calibration curve was linear in the range of 1.0 ng mL⁻¹-0.6 μg mL⁻¹ of copper with R² = 0.9985. Detection limit was 0.5 ng mL⁻¹ in original solution (3S_b/m) and the relative standard deviation for seven replicate determination of 0.2 μg mL⁻¹ copper was ±1.4%. The proposed method has been applied for determination of copper in standard and water samples with satisfactory results.     

Sensitive determination of hydrazine in water by gas chromatography–mass spectrometry after derivatization with ortho-phthalaldehyde

A gas chromatography–mass spectrometric (GC–MS) method has been established for the determination of hydrazine in drinking water and surface water. This method is based on the derivatization of hydrazine with ortho-phthalaldehyde (OPA) in water. The following optimum reaction conditions were established: reagent dosage, 40 mg mL⁻¹ of OPA; pH 2; reaction for 20 min at 70 °C. The organic derivative was extracted with methylene chloride and then measured by GC–MS. Under the established condition, the detection and the quantification limits were 0.002 μg L⁻¹ and 0.007 μg L⁻¹ by using 5.0-mL of surface water or drinking water, respectively. The calibration curve showed good linearity with r² = 0.9991 (for working range of 0.05–100 μg L⁻¹) and the accuracy was in a range of 95–106%, and the precision of the assay was less than 13% in water. Hydrazine was detected in a concentration range of 0.05–0.14 μg L⁻¹ in 2 samples of 10 raw drinking water samples and in a concentration range of 0.09–0.55 μg L⁻¹ in 4 samples of 10 treated drinking water samples.     

Modified iron oxide nanoparticles as solid phase extractor for spectrophotometeric determination and separation of basic fuchsin

This study presents a novel separation, preconcentration and determination of basic fuchsin (BF) in an aqueous solution by sodium dodecyl sulfate (SDS)-bounded iron oxide nanoparticles (S-IONPs). It is shown that the novel magnetic nano-adsorbent is quite efficient for the adsorption and desorption of BF at 25 °C. Different parameters such as pH, temperature, ionic strength and composition of desorbent solvent were optimized. The effect of some co-existing ions on the determination was investigated. The nanoparticles were analyzed by transmission electron microscopy (TEM) and the sizes of S-IONPs were in the range of 20-100 nm. The method showed good linearity for the determination of BF in the range of 10-300 ng mL⁻¹ with a regression coefficient of 0.9989. The limit of detection (LOD) (signal-to-noise ratio of 3:1) was 0.0073 μg L⁻¹ and the relative standard deviation (RSD) for 0.03 μg mL⁻¹ and 0.2 μg mL⁻¹ of BF were 4.53% and 4.73%, respectively. The BF was determined successfully in spiked samples of Karoon River water.     

A simple and green analytical method for determination of iron based on micro flow analysis

A simple, inexpensive and reagent-less colorimetric micro flow analysis (μFA) system was implemented in a polymethyl methacrylate (PMMA) micro fluidic manifold. A T-shaped micro channel on a PMMA chip was fabricated by laser ablation and topped with molded polydimethylsiloxane (PDMS). The fabricated μFA system was integrated with the optical components as detector and applied to the determination of iron in water samples. It is based on the measurement of Fe(III)-nitroso-R salt complex at 720 nm formed by the reaction between Fe(III) and nitroso-R salt in an acetate buffer solution pH 5. The proposed μFA consumed very small amount of reagent and sample, it released waste of less than 2.0 mL h⁻¹. The relative standard deviation (R.S.D.) was less than 2% (n = 11) with the recovery of 98.7 ± 0.12 (n = 5). The linear range for the determination of iron in water samples was over the range of 0.05-4.0 μg mL⁻¹ with a correlation coefficient (r²) of 0.9994. The limit of detection (3σ) and limit of quantitation (10σ) were 0.021 μg mL⁻¹ and 0.081 μg mL⁻¹, respectively with a sample throughput of 40 h⁻¹.     

Determination of mono- and dichloroacetic acids in betaine media by liquid chromatography

A simple and sensitive method has been developed for the analysis of residue amounts of chloroacetic acids in betaine samples based on derivatization by 1-naphthylamine (NA). The derivatized compounds are analyzed by reverse phase high performance liquid chromatography using methanol and water as mobile phase in the ratio of 32/68 (v/v) and phenyl column and PDA detection at 222 nm. The detection limits (LOD) of monochloroacetic acid (MCA) and dichloroacetic acid (DCA) are 0.1 and 0.15 μg mL⁻¹, respectively. The limits of quantification (LOQ) and the linear dynamic ranges (LDR) of MCA are found to be 1 and 1-400 μg mL⁻¹, respectively, and for DCA are found to be 3 and 3-400 μg mL⁻¹, respectively. The precision at the 5 ppm level for MCA and DCA are about 3% and 2%, (n = 5), respectively. The average recovery for MCA and DCA spiked to betaine samples are 98% and 97%, respectively.     

Catalysis reaction between sodium 1,2-naphthoquinone-4-sulfonate and hydroxyl ion using captopril as catalyzer and determination of captopril

A novel and simple spectrophotometric method for the determination of Captopril with sodium 1,2-naphthoquinone-4-sulfonate is established in this paper. The detailed reaction mechanism is proposed and discussed. It is based on the fact that captopril can catalyze the reaction between sodium 1,2-naphthoquinone-4-sulfonate and hydroxyl ion to form 2-hydroxy-1,4-naphthoquinone in buffer solution of pH 13.00. Beer's law is obeyed in a range of 0.64-80 μg mL⁻¹ at the maximal absorption wavelength of 442 nm. The equation of linear regression is A = 0.05815 + 0.00589C (μg mL⁻¹), with a linear regression correlation coefficient of 0.9981. The detection limit is 0.3 μg mL⁻¹, R.S.D. is 0.77% and the recovery rate is in range of 96.0-103.8%. Furthermore, the method has been validated and successfully applied to the determination of captopril in pharmaceutical samples.     

Headspace liquid-phase microextraction using ionic liquid as extractant for the preconcentration of dichlorodiphenyltrichloroethane and its metabolites at trace levels in water samples

A novel technique, high temperature headspace liquid-phase microextraction (HS-LPME) with room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄MIM][PF₆]) as extractant, was developed for the analysis of dichlorodiphenyltrichloroethane (p,p′-DDT and o,p′-DDT) and its metabolites including 4,4′-dichlorodiphenyldichloroethylene (p,p′-DDE) and 4,4′-dichlorodiphenyldichloroethane (p,p′-DDD) in water samples by high performance liquid chromatography with ultraviolet detection. The parameters such as salt content, sample pH and temperature, stirring rate, extraction time, microdrop volume, and sample volume, were found to have significant influence on the HS-LPME. The conditions optimized for extraction of target compounds were as follows: 35% NaCl (w/v), neutral pH condition, 70 °C, 800 rpm, 30 min, 10 μL [C₄MIM][PF₆], and 25 mL sample solutions. Under the optimized conditions, the linear range, detection limit (S/N = 3), and precision (R.S.D., n = 6) were 0.3-30 μg L⁻¹, 0.07 μg L⁻¹, and 8.0% for p,p′-DDD, 0.3-30 μg L⁻¹, 0.08 μg L⁻¹, and 7.1% for p,p′-DDT, 0.3-30 μg L⁻¹, 0.08 μg L⁻¹, and 7.2% for o,p′-DDT, and 0.2-30 μg L⁻¹, 0.05 μg L⁻¹, and 6.8% for p,p′-DDE, respectively. Water samples including tap water, well water, snow water, reservoir water, and wastewater were analyzed by the proposed procedure and the recoveries at 5 μg L⁻¹ spiked level were in the range of 86.8-102.6%.     

A reversed-phase high performance liquid chromatography coupled with resonance Rayleigh scattering detection for the determination of four tetracycline antibiotics

A new reversed-phase high performance liquid chromatography with resonance Rayleigh scattering detection (HPLC-RRS) was developed for simultaneous separation and determination of four tetracycline antibiotics (TCs). A good chromatographic separation among the compounds was achieved using a Synergi Fusion-RP column (150 mm × 4.6 mm; 4 μm) and a mobile phase consisting of methanol-acetonitrile-oxalic acid (5 mM) at the flow rate of 0.8 mL min⁻¹. Column temperature was 30 °C. The RRS signal was detected at λ_ex = λ_em = 370 nm. The recoveries of sample added standard ranged from 95.3% to 103.5%, and the relative standard deviation was below 2.79%. A detection limit of 2.12-5.12 μg mL⁻¹ was reached and a linear range was found between peak height and concentration in the range of 10.36-518.0 μg mL⁻¹ for oxytetracycline (OTC), 12.11-605.5 μg mL⁻¹ for tetracycline (TC), 11.79-589.5 μg mL⁻¹ for chlortetracycline (CTC) and 10.32-516.0 μg mL⁻¹ for doxycycline (DC). The linear regression coefficients were all above 0.999. The method has been applied successfully to the determination of OTC, TC, CTC, DC in pharmaceutical formulations and in honey. The method was simple, rapid and showed a better linear relation and high repeatability.     

Simultaneous cloud point extraction and spectrophotometric determination of carmoisine and brilliant blue FCF in food samples

A novel simultaneous cloud point extraction method for the determination of carmoisine and brilliant blue FCF by spectrophotometry has been developed. The method is based on the cloud point extraction of carmoisine and brilliant blue FCF from aqueous solution using Triton X-100, diluting the extracted surfactant rich phase with water and measuring the absorbance at 522 and 640 nm for carmoisine and brilliant blue FCF, respectively. The effects of different parameters such as pH, concentration of surfactant and temperature on the cloud point extraction of both dyes were investigated and optimum conditions were established. Linear calibration curves were obtained in the range of 0.02-3.50 μg mL⁻¹ for carmoisine and 0.05-3.50 μg mL⁻¹ for brilliant blue FCF under optimum conditions. Detection limit based on three times the standard deviation of the blank (3S_b) was 0.017 and 0.016 μg mL⁻¹ (n = 10) for carmoisine and brilliant blue FCF, respectively. The relative standard deviation (RSD) for 0.1 μg mL⁻¹ was 4.14 and 3.30% (n = 10), for carmoisine and brilliant blue FCF, respectively. The method was applied to the simultaneous determination of the dyes in different food samples.     

Simultaneous analysis of anionic, amphoteric, nonionic and cationic surfactant mixtures in shampoo and hair conditioner by RP-HPLC/ELSD and LC/MS

A simple and simultaneous analysis method for four (anionic, amphoteric, nonionic, and cationic) classes of surfactants in shampoo and hair conditioner was newly developed. Analysis of the surfactants was performed using a reversed-phase HPLC (RPLC) combined with evaporative light scattering detection (ELSD) without any pre-treatment. An optimum analysis condition for the resolution of both four main surfactant mixtures used in shampoo and five main surfactants used in hair conditioner could be established under a gradient mobile phase condition with acetonitrile, tetrahydrofuran and water. The detection limits were 2.5-30 μg mL⁻¹ except for SLES (150 μg mL⁻¹), and the calibration curves, i.e. the log-log plots, were linear in the working range of 2.5-5250 μg mL⁻¹ with R² values of above 0.998. The observed precision was less than 5% R.S.D. The elution peaks were identified by a liquid chromatography-mass spectrometer (LC-MS) equipped with an electrospray interface operating in mixed-mode.     

Gas chromatographic determination of carbonyl compounds in biological and oil samples by headspace single-drop microextraction with in-drop derivatisation

A suitable method for the gas chromatographic determination of 10 characteristic carbonyls in biological and oil samples based on the in-drop formation of hydrazones by using 2,4,6-trichlorophenylhydrazine (TCPH), has been developed. The derivatisation-extraction procedure was optimized separately for aqueous and oil samples with respect to the appropriate organic drop solvent, drop volume, in-drop TCPH concentration, sample stirring rate, temperature during single-drop microextraction (SDME), reaction time and headspace-to-sample volume ratio. The optimization showed differentiation of optimum values between the studied matrices. The limits of detection were found to range from 0.001 to 0.003 μg mL⁻¹ for the aqueous biological samples and from 0.06 to 0.20 μg mL⁻¹ for the oil samples. The limits of quantification were in the range of 0.003-0.010 μg mL⁻¹ and 0.020-0.059 μg mL⁻¹ for aqueous and oil samples, respectively. The overall relative standard deviations of the within-day repeatability and between-day reproducibility were <4.4% and <8.2% for the aqueous biological samples and <3.9% and <7.4% for the oxidized oil samples.     

Determination of andrographolide and dehydroandrographolide in rabbit plasma by on-line solid phase extraction of high-performance liquid chromatography

The high-performance liquid chromatography (HPLC) coupled with on-line solid phase extraction (SPE) and ultraviolet (UV) detection was developed for determining andrographolide and dehydroandrographolide in rabbit plasma. Plasma samples (100 μL) were injected directly into a C18 SPE column and the biological matrix was washed out for 6 min using 15% aqueous methanol. By rotation of the switching valve, andrographolide and dehydroandrographolide were eluted in the back-flush mode and transferred to the analytical column by the chromatographic mobile phase consisted of methanol:acetonitrile (ACN):water (50:10:40; v/v). The UV detection was performed at 225 nm. The calibration curves showed excellent linear relationship (R ≥ 0.9993) over the concentration range of 0.05-5.0 μg mL⁻¹. The within- and between-day precisions (R.S.D.) of two analytes were in the range of 1.2-6.5% and the accuracies were between 92.0% and 102.1%. Their recoveries were all greater than 94%. The limits of detection were 0.019 μg mL⁻¹ for andrographolide and 0.022 μg mL⁻¹ for dehydroandrographolide. This method was successfully applied to the plasma concentration-time curve study after oral administration of Andrographis paniculata Nees extract in rabbit.     

Development, validation and application of a SDME/GC-FID methodology for the multiresidue determination of organophosphate and pyrethroid pesticides in water

A single-drop microextraction (SDME) procedure was developed for the analysis of organophosphorus and pyrethroid pesticides in water by gas chromatography (GC) with flame ionization detection (GC-FID). The significant parameters that affect SDME performance, such as the selection of microextraction solvent, solvent volume, extraction time, and stirring rate, were studied and optimized using a tool screening factorial design. The limits of detection (LODs) in water for the four investigated compounds were between 0.3 and 3.0 μg L⁻¹, with relative standard deviations ranging from 7.7 to 18.8%. Linear response data were obtained in the concentration range of 0.9-6.0 μg L⁻¹ (λ-cyhalothrin), 3.0-60.0 μg L⁻¹ (methyl parathion), 9.0-60.0 μg L⁻¹ (ethion), and 9.0-30.0 μg L⁻¹ (permethrin), with correlation coefficients ranging from 0.9337 to 0.9977. The relative recoveries for the spiked water ranged from 73.0 to 104%. Environmental water samples (n = 26) were successfully analyzed using the proposed method and methyl parathion presented concentration up to 2.74 μg L⁻¹. The SDME method, coupled with GC-FID analysis, provided good precision, accuracy, and reproducibility over a wide linear range. Other highlights of the method include its ease of use and its requirement of only small volumes of both organic solvent and sample.     

In-syringe demulsified dispersive liquid–liquid microextraction and high performance liquid chromatography–mass spectrometry for the determination of trace fungicides in environmental water samples

An in-syringe demulsified dispersive liquid–liquid microextraction (ISD–DLLME) technique was developed using low-density extraction solvents for the highly sensitive determination of the three trace fungicides (azoxystrobin, diethofencarb and pyrimethanil) in water samples by high performance liquid chromatography–mass spectrometry chromatography–diode array detector/electrospray ionisation mass spectrometry. In the proposed technique, a 5-mL syringe was used as an extraction, separation and preconcentration container. The emulsion was obtained after the mixture of toluene (extraction solvent) and methanol (dispersive solvent) was injected into the aqueous bulk of the syringe. The obtained emulsion cleared into two phases without centrifugation, when an aliquot of methanol was introduced as a demulsifier. The separated floating organic extraction solvent was impelled and collected into a pipette tip fitted to the tip of the syringe. Under the optimal conditions, the enrichment factors for azoxystrobin, diethofencarb and pyrimethanil were 239, 200, 195, respectively. The limits of detection, calculated as three times the signal-to-noise ratio (S N⁻¹), were 0.026 μg L⁻¹ for azoxystrobin, 0.071 μg L⁻¹ for diethofencarb and 0.040 μg L⁻¹ for pyrimethanil. The repeatability study was carried out by extracting the spiked water samples at concentration levels of 0.02 μg mL⁻¹ for all the three fungicides. The relative standard deviations varied between 4.9 and 8.2% (n = 5). The recoveries of all the three fungicides from tap, lake and rain water samples at spiking levels of 0.2, 1, 5 μg L⁻¹ were in the range of 90.0–105.0%, 86.0–114.0% and 88.6–110.0%, respectively. The proposed ISD–DLLME technique was demonstrated to be simple, practical and efficient for the determination of different kinds of fungicide residues in real water samples.     

Electropolymerized multiwalled carbon nanotubes/polypyrrole fiber for solid-phase microextraction and its applications in the determination of pyrethroids

A novel solid-phase microextraction (SPME) fiber coated with multiwalled carbon nanotubes/polypyrrole (MWCNTs/Ppy) was prepared with an electrochemical method and used for the extraction of pyrethroids in natural water samples. The results showed that the MWCNTs/Ppy coated fiber had high organic stability, and remarkable acid and alkali resistance. In addition, the MWCNTs/Ppy coated fiber was more effective and superior to commercial PDMS and PDMS/DVD fibers in extracting pyrethroids in natural water samples. Under optimized conditions, the calibration curves were found to be linear from 0.001 to 10 μg mL⁻¹ for five of the six pyrethroids studied, the exception being fenvalerate (which was from 0.005 to 10 μg mL⁻¹), and detection limits were within the range 0.12-0.43 ng mL⁻¹. The recoveries of the pyrethroids spiked in water samples at 10 ng mL⁻¹ ranged from 83 to 112%.