Sequential Injection Magneto Chromatography Determination of Non-Steroidal Anti-Inflammatory Drugs in Pharmaceutical Formulations

A magnetic separation method based on the use of magnetic silica as the stationary phase in sequential injection chromatography was used for simultaneous determination of nonsteroidal anti-inflammatory drugs (acetaminophen, naproxen, diclofenac, and ibuprofen) in tablets. The method is based on a thin layer paramagnetic stationary phase retained on the inner wall of a mini-column through the action of an external magnetic field. The influence of the variables involved was evaluated and the optimal conditions were found to be: a methyl-silica magnetic adsorbent was used as the stationary phase, the mobile phase was methanol-water (60:40, v/v), pH 2.5 adjusted with 98% phosphoric acid, a flow rate 0.60 ml min^?1, and UV detection at 225 nm. Under these conditions, the linear range of the calibration curve ranged from 3–6 mg L^?1 to 100 mg L^?1 with limits of detection ranging between 1 to 2 mg L^?1. The proposed method was validated by comparing the results obtained against those provided by high performance liquid chromatography; no significant differences were seen.     

Improving the Determination of Nitrovin in Feeds by Reversed-Phase LC with SPE

A simple reversed-phase liquid chromatographic method with ultraviolet detector (378 nm) for the determination of nitrovin in feeds was improved and validated. The mobile phase was a mixture of acetonitrile and 0.1% formic acid solution (v/v) in the ratio of 50:50 (v/v), and the flow rate was set at 1.2 mL min^?1. The extraction solution was a mixture of dimethyl formamide, acetonitrile and methanol (50:25:25, v/v), the sample was cleaned-up with reversed-phase solid phase extraction cartridge. The standard nitrovin was purified with crude nitrovin product by ethylene glycol monoethyl ether and identified by elemental analyzer. The limit of detection was 0.05 mg kg^?1 and the limit of quatification was 0.2 mg kg^?1 in feeds. The assay had satisfactory selectivity, recovery, linearity and precise repeatability and trueness.     

Resolution of Racemic Ofloxacin Based on Co-Technology of Bubble Fractionation and Extraction

A method of bubble fractionation, with the help of solvent extraction, was developed for the resolution of racemic ofloxacin (rac OFLX). In this method, dibenzoyl-L-tartaric (L-DBTA), di-(2-ethylhexyl) phosphoric acid (D2EHPA) and sodium lauryl sulfate (SDS) were used as chiral collector, co-extractant and foamer, respectively. Several important parameters influencing the resolution performances, such as pH in aqueous phase, concentration of OFLX, concentration of L-DBTA, concentration of SDS and volume ratio of D2EHPA to n-octanol in solution, were investigated. The optimal resolution conditions were obtained with the aqueous phase pH 7, volume ratio of D2EHPA to n-octanol 6/14 in organic phase, concentration of SDS 0.42 mg mL^?1, concentration of OFLX 1.67 mg mL^?1, and concentration of L-DBTA 0.11 g mL^?1. Under the optimal extraction conditions, the enantiomeric excess value (e.e.%) was 60.08% and the enantioselectivity (??) was 5.58. It was found that the capacity of enantioselective separation can be greatly improved by the co-technology.     

Simultaneous CE Determination of Captopril and Indapamide in Pharmaceuticals and Human Plasma

Capillary electrophoresis with UV photo diode-array detection was utilized to adopt a new method for the assay of captopril and indapamide in pharmaceuticals and human plasma. Electrophoretic conditions controlling the analysis were optimized to develop separation, sensitivity and rapidity. The optimum conditions obtained were 100 mM borate at pH 9.0, injection time 10.0 s, voltage 25 kV and column temperature 25 °C with detection at 220 nm. Relatively, wide dynamic ranges for captopril (1–100 mg L^?1) and indapamide (0.1–40 mg L^?1) were obtained. Also, the method recorded acceptable intra- and inter-day accuracy (89.8–97.9%) and precision (0.77–3.50%) in pharmaceutical formulations and human plasma. The sensitivity of the method was developed by the optimization and the preconcentration conducted for human plasma sample using liquid–liquid extraction. The limit of detection gained (0.075 and 0.045 mg L^?1 for captopril and indapamide, respectively) reached the level of both drugs possibly found in human plasma. The method is suitable to be applied in pharmaceutical industries for quality control and in clinical laboratories for therapeutic drug monitoring purposes.     

Determination of Sb(III) and Total Sb in Antileishmanial Drugs by Spectrophotometric Flow‐Injection Hydride Generation

Abstract

A spectrophotometric procedure based on hydride generation and flow analysis is proposed for determination of antimony (III) [Sb(III)] and total antimony (Sb) in pharmaceutical samples. Firstly, Sb(III) reacts with hydrogen species generated in the system, forming antimony hydride. The reaction leads to a decrease in the permanganate concentration and, hence, in the intensity of the color of this specie, which is spectrophotometrically measured at 528 nm. Total Sb is determined as Sb(III) after Sb(V) reduction using 0.02% (m/v) KI. Some parameters, such as the number of channels of the gas phase separator, injection volume, coil length, and KBH₄ concentration, are investigated. The system presents a frequency of ca. 100 h^?1 and precision <3.0% [expressed as relative standard deviation (RSD) of 30 measurements using a 3.0 mg L^?1 Sb(III) solution]. The analytical curve ranging from 0.5 mg L^?1 to 5.0 mg L^?1 (r>0.998; n=5) permits limit of detection (LOD) and limit of quantification (LOQ) of 83 and 250 µg L^?1. For total Sb, the accuracy is checked by atomic absorption spectrometry applying the t test and the results are in accordance at the 95% confidence level. Recovery tests are used to check the accuracy for Sb(III) determination, and the recoveries are between 95% and 105%.     

Temperature-assisted ionic liquid-based dispersive liquid–liquid microextraction with following back-extraction for HPLC/UV–Vis determination of 3-indole acetic acid in pea plants

In this work, the ionic liquid (IL)[C₆mim][PF₆] was used as IL-based extractant for dispersive liquid–liquid microextraction, followed by back-extraction and HPLC/UV–Vis determination of 3-indole acetic acid (IAA) in pea plant. The effects of some crucial factors such as chemical structure and volume of IL, pH adjustment, dissolution temperature, extraction time, centrifugation time, and ionic strength of aqueous sample were studied. The linear range of the HPLC method for IAA quantification was 17.5 × 10^?2–36.8 mg L^?1. LOD, LOQ, method recovery, and preconcentration factor values were 0.170 mg L^?1, 0.175 mg L^?1, 98.3, and 40 %, respectively. The RSD for the suggested method was calculated as 0.93 % at 35.04 mg L^?1 of IAA and each IL phase was able to be reused for at least four DLLME/back-extraction cycles. To evaluate the applicability of the suggested method, IAA was determined in pea plant samples.     

Simultaneous Derivatization and Dispersive Liquid–Liquid Microextraction for Fatty Acid GC Determination in Water

Simultaneous derivatization and dispersive liquid–liquid microextraction technique for gas chromatographic determination of fatty acids in water samples is presented. One hundred microlitre of ethanol:pyridine (4:1) were added to 4 mL aqueous sample. Then a solution containing 0.960 mL of acetone (disperser solvent), 10 μL of carbon tetrachloride (extraction solvent) and 30 μL of ethyl chloroformate (derivatization reagent) were rapidly injected into the aqueous sample. After centrifugation, 1 μL sedimented phase with the analytes was analyzed by gas chromatography. The effects of extraction solvent type, derivatization, extraction, and disperser solvents volume, extraction time were investigated. The calibration graphs were linear up to 10 mg L^?1 for azelaic acid (R ² = 0.998) and up to 1 mg L^?1 for palmitic and stearic acids (R ² = 0.997). The detection limits were 14.5, 0.67 and 1.06 μg L^?1 for azelaic, palmitic, and stearic acids, respectively. Repeatabilities of the results were acceptable with relative standard deviations (RSD) up to 13%. A possibility to apply the proposed method for fatty acids determination in tap, lake, sea, and river water was demonstrated.     

Multivariate Optimization and Validation of a CZE Method for the Analysis of Pridinol Mesylate and Meloxicam in Tablets

A capillary zone electrophoresis method for the simultaneous determination of pridinol mesylate (PRI) and meloxicam (MEL) employing epinastine hydrochloride and piroxicam as internal standards, was developed and optimized employing experimental design and response surface methodologies. The separation was optimally achieved in less than 2 min at 30 kV in an uncoated fused-silica capillary (41.4 cm × 75 ??m I.D.), employing an 18 mmol L^?1 sodium phosphate buffer solution (pH 5.90) at 25 °C. Samples were injected in hydrodynamic mode (50 mbar, 5 s) and the analytes were spectrophotometrically detected at 200 nm. Method robustness was demonstrated by ANOVA of determinations performed under conditions slightly different from the optimum. The method was validated regarding separation selectivity (peak purity factors > 0.99), linearity and range (PRI = 17.6?C31.4 mg L^?1; MEL = 66.5?C122.5 mg L^?1), accuracy (PRI = 100.2?C101.9%; MEL = 98.9?C100.7%) and precision. The RSD values obtained were ??1.3% for injection repeatability and ??1.9% for intra-day precision. The limits of detection (1.0 and 0.9 mg L^?1) and quantification (3.3 and 16.5 mg L^?1) of PRI and MEL, respectively, were also determined. The method was successfully applied to the determination of both drugs in three brands of tablet formulations. No statistically significant differences were observed when these results were compared with those of a RP-HPLC method.     

Determination of tetracyclines in milk samples by magnetic solid phase extraction flow injection analysis

A method is presented for magnetic solid phase extraction (MSPE) of tetracyclines in milk samples. The method involves the extraction and clean-up by silica based magnetic support dispersion on non-pretreated milk samples, followed by the magnetic isolation and desorption of the analytes by acidified methanol. The tetracyclines eluted from the magnetic support were determined simultaneously by flow injection analysis with spectrophotometric detection. Under optimal conditions, the linear range of the calibration curve ranges from 0.03 to 0.60 mg L^?1, with a limit of detection of 10 μg L^?1. Recoveries were determined for milk spiked at levels from 0.15 to 0.60 mg L^?1. Average recoveries ranged from 91.0 to 97.0%, with a precision of <5.0% in all cases. The method was validated by comparing the results with those obtained by MSPE-HPLC and SPE-HPLC. No significant differences were observed (p?<?0.05)     

Semi-automated cloud point extraction with cold column trapping of surfactant-rich phase for phenazopyridine determination in human serum

A semi-automated cold column trapping-cloud point extraction (CCT-CPE) method was developed and applied to the determination of phenazopyridine in human serum. In the proposed technique, a mixture of sample (pH 8) and Triton X-100 (0.4 % v/v) was incubated at 90 °C for 5 min in a heating sample cell. The developed turbid solution was then flowed through a CCT preconcentration column packed with C18 sorbent using a peristaltic pump. A pair of thermal electric cooler (TEC) plates was used for cooling the column. The surfactant-rich phase was retained on the CCT at 0 °C and desorbed, subsequently, in an elevated temperature by ethanol. The analytical parameters such as pH, surfactant concentration, temperature and incubation time were optimized by a central composite design (response surface) method. Six replicated analyses at the optimized conditions resulted in a recovery of 99.7 % and a relative standard deviation of 2.45 for phenazopyridine. The detection limit of the method (3σ) was 0.50 mg L^?1 for the analyte. Compared to conventional CPE, the proposed CCT-CPE method required less sample handling, eliminated the centrifugation step and was substantially faster. The method was successfully applied to the determination of phenazopyridine in some human serum and tablet samples.     

Liquid–liquid microextraction and spectrophotometric determination of anionic surfactants using Astra Phloxine FF

A novel and simple procedure for determination of anionic surfactants has been developed. The method is based on the reaction of sodium dodecyl sulphate (SDS) with Astra Phloxine FF reagent at pH 3–8, followed by liquid–liquid microextraction of the formed ion associate into an organic phase containing a mixture of carbon tetrachloride and dichloroethane (4:1, v/v) and subsequent UV-Vis detection at 555 nm. The calibration plot was linear in the range 0.006–0.29 mg L^?1 of SDS. The limit of detection (LOD), calculated based on 3s, is 0.002 mg L^?1. The method was applied to the determination of anionic surfactants in real wastewater samples.     

LC�CMS�CMS Method for Quantification of Hydralazine in BALB/C Mouse Plasma and Brain: Application to Pharmacokinetic Study

A rapid, sensitive and accurate high performance liquid chromatography method using tandem mass spectrometry detection for hydralazine in BALB/C mouse plasma and brain was developed and validated. The method involved a derivatization with 2,4-pentanedione at 50 °C for 1 h, and a step of solid phase extraction to purify and concentrate hydralazine derivative. Chromatographic separation was carried out on an Agilent ZORBAX SB-C18 column by elution with methanol?C0.01 mol L^?1 ammonium acetate (60:40, v/v). The multiple reaction monitoring transition used for quantification was m/z 225.2 ?? 129.5 in the electrospray positive ionization mode. Good linearity was obtained over the concentration range of 10?C200 ng mL^?1. The limits of detection were 0.49 and 1.05 ng mL^?1 for hydralazine in mouse plasma and brain, respectively. The limits of quantitation were 1.5 and 3.18 ng mL^?1 for hydralazine in mouse plasma and brain, respectively. Sample analysis time was 6 min including sample separation. The method was successfully applied to a pharmacokinetic study following intraperitoneal injection of hydralazine in BALB/C mice at the dose of 20 mg kg^?1.     

Determination of Trenbolone Acetate in Cattle Feeds by a Flow Injection Chemiluminescence Method

A flow injection chemiluminescence (CL) method is described for the determination of trenbolone acetate based on the CL generated during its reaction with KMnO₄ in acidic medium. The CL intensity is greatly enhanced by alizarin yellow R. The CL intensity is linear with trenbolone acetate concentration in the range 0.1–100.0 mg L^?1 with a detection limit of 0.05 mg L^?1. The sample throughout is about 90 h^?1 and the relative standard deviation for 2.0 mg L^?1 trenbolone acetate solution is 1.5% (n = 11). The proposed method was applied to the determination of trenbolone acetate in cattle feeds.     

Extraction of Azole Antifungal Drugs from Milk and Biological Fluids Using a New Hollow Fiber Liquid-Phase Microextraction and Analysis by GC-FID

A simple, rapid and sensitive high-performance liquid chromatography LC (HPLC) method of determining the concentration of the novel betulinic acid derivative DRF-4012 (5??-chloro-2,3-didehydroindolo[2??,3??:2,3]betulinic acid) in rat plasma for pharmacokinetic and toxicokinetic purposes has been developed and validated. A simple and fast protein precipitation was performed, and then an extraction using an ethyl acetate:methanol (75:25 v/v) mixture was used to extract DRF-4012 and an internal standard (IS, DRF-4015) from rat plasma. Chromatographic separation was achieved using a Zorbax Eclipse XDB-C8 reversed-phase column with UV detection at 235 nm. The isocratic mobile phase, phosphate buffer (water adjusted to pH 3 with 20% o-phosphoric acid) and acetonitrile (15:85, v/v), was run at a flow rate of 1.2 mL min^?1. The assay was linear (r ² > 0.99) over the concentration range 0.040?C75.0 ??g mL^?1, and presented limits of detection and quantification of 0.020 and 0.040 ??g mL^?1, respectively, in rat plasma. The absolute recovery of both the analyte and the IS was >85% from rat plasma. The intraday accuracy ranged from 99.25 to 102.67% with a precision of 2.62?C4.48%, and the interday accuracy ranged from 98.48 to 104.56% with a precision of 3.87?C5.68%. This developed and validated method was successfully used to determine the DRF-4012 concentration in rat plasma for a pharmacokinetic and toxicokinetic study after the intravenous administration of a 1 mg mL^?1 DRF-4012 nanoparticle formulation at doses of 2?C10 mg kg^?1 in Wistar rats.     

Ionic Liquid-Based Ultrasonic/Microwave-Assisted Extraction Combined with UPLC for the Determination of Anthraquinones in Rhubarb

Ionic liquid-based ultrasonic/microwave-assisted extraction (IL-UMAE) of five anthraquinones (physcion, chrysophanol, emodin, rhein, and aloe-emodin) from rhubarb was first studied. Several parameters of UMAE were optimized, and the results were compared with of the heat-reflux extraction (HRE), ultrasound, and microwave-assisted extraction (MAE and UAE). The optimal UMAE conditions were as follows: the solvent was 2.0 mol L^?1 1-butyl-3-methylimidazolium bromide [bmim]Br solution, the ration of solid/liquid (g mL^?1) was 1:15, time was 2 min, and microwave power was 500 W. Under these UMAE conditions, total content of five anthraquinones was 28.00 mg g^?1. Compared with the conventional HRE, regular MAE and UAE techniques, the proposed approach exhibited higher efficiency (18.90?C24.40% enhanced) and shorter extraction time (from 6 h to 2 min). The anthraquinones were then determined by ultra performance liquid chromatography (UPLC). Based on optimized conditions, contents of physcion, chrysophanol, emodin, rhein and aloe-emodin in rhubarb collected from different cultivated areas were 0.68?C2.99, 5.03?C15.40, 0.48?C4.34, 0.025?C3.93 and 0.26?C2.56 mg g^?1, respectively. This study suggests that IL-UMAE was an efficient, rapid, simple and green preparation technique.     

Homogeneous Liquid–Liquid Microextraction for Determination of Organochlorine Pesticides in Water and Fruit Samples

A fast and effective preconcentration method for extraction of organochlorine pesticides (OCPs) was developed using a homogeneous liquid–liquid extraction based on phase separation phenomenon in a ternary solvent (water/methanol/chloroform) system. The phase separation phenomenon occurred by salt addition. After centrifugation, the extraction solvent was sedimented in the bottom of the conical test tube. The OCPs were transferred into the sedimented phase during the phase separation step. The extracted OCPs were determined using gas chromatography–electron capture detector. Several factors influencing the extraction efficiency were investigated and optimized. Optimal results were obtained at the following conditions: volume of the consolute solvent (methanol), 1.0 mL; volume of the extraction solvent (chloroform), 55 μL; volume of the sample, 5 mL; and concentration of NaCl, 5 % (w/v). Under optimal conditions, the preconcentration factors in the range of 486–1,090, the dynamic linear range of 0.01–100 μg L^?1, and the limits of detection of 0.001–0.03 μg L^?1 were obtained for the OCPs. Using internal standard, the relative standard deviations for 1 μg L^?1 of the OCPs in the water samples were obtained in the range of 4.9–8.6 % (n = 5). Finally, the proposed method was successfully applied for extraction and determination of the OCPs in water and fruit samples.     

A stir foam composed of graphene oxide,poly(ethylene glycol) and natural latex for the extraction of preservatives and antioxidant

A stir foam composed of graphene oxide, poly(ethylene glycol) and natural latex (GO-PEG-NL) was prepared for use in micro-solid phase extraction sorbent of preservative agents and antioxidants from cosmetic products. The extracted analytes were quantified by GC-MS. Under the optimized conditions, the calibration plots are linear in the concentration ranges between 5.0 μg·L^?1 to 1.0 mg·L^?1 for benzoic acid, of 10.0 μg·L^?1 to 1.0 mg·L^?1 for 2-methyl-3-isothiazolinone (MI), and between 1.0 μg·L^?1 and 1.0 mg·L^?1 for both 3-tert-butyl-4-hydroxyanisole (BHA) and 2,6-di-tert-butyl-p-hydroxytoluene (BHT). The LODs are 1.0 μg·L^?1 for benzoic acid, 5.0 μg·L^?1 for MI and 0.5 μg·L^?1 for both BHA and BHT. The stir-foam can be easily prepared, is inexpensive and well reproducible (RSDs <3%, for n?=?6). It can be re-used for up to 12 times after which extraction efficiency has dropped to 90%. The method was successfully applied to the determination of preservatives and antioxidants in cosmetic samples. Recoveries from spiked samples ranged between 94.5?±?2.1% and 99.8?±?1.8%.

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Graphical abstract A stir foam was prepared from graphene oxide, poly(ethylene glycol) and natural latex (GO-PEG-NL) and is shown to be a most viable sorbent for the microextraction of trace amounts of preservative agents and antioxidants from cosmetic products.

     

Preconcentration and spectrophotometric determination of trace amount of formaldehyde using hollow fiber liquid-phase microextraction based on derivatization by Hantzsch reaction

Formaldehyde is known as a highly toxic compound to humans and identified as a carcinogenic substance. In this study, Hantzsch reaction was utilized for the derivatization of trace amounts of formaldehyde in aqueous samples with acetylacetone in the presence of ammonia to form an extractable colored product named 3,5-diacetyl 1,4-dihydrolutidine (DDL) and its further extraction using two-phase hollow fiber liquid-phase microextraction. The main experimental variables affecting the extraction performance were investigated and optimized. Under the optimum conditions (sample volume 12 mL; reaction temperature 70 °C; ammonium acetate buffer solution 4 mL 0.1 mol L^?1; acetylacetone 5 mL 0.15 mol L^?1; solvent octanol, salt concentration 20% (w/v) NaCl; pH of donor phase 7.0; stirring speed 400 rpm and extraction time 30 min), the linear dynamic range, limit of detection (LOD as 3S _b/m) and relative standard deviation (RSD %) of the proposed method were obtained as 5–250 μg L^?1 (r ² = 0.9979), 3.6 μg L^?1 and 2.5%, respectively. Finally, the applicability of the proposed method was examined, and very good results were obtained. The results confirmed the applicability of the proposed method as a versatile, low-cost and sensitive preconcentration method for determination of low concentrations of formaldehyde in aqueous solutions.     

Magnetic solid-phase extraction of Zineb by C18-functionalised paramagnetic nanoparticles and determination by first-derivative spectrophotometry

Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles have been synthesised and used as magnetic solid-phase extraction (MSPE) sorbent for the extraction of Zineb from agricultural aqueous samples under ultrasonic condition and quantified through a first-derivative spectrophotometric method. The produced magnetic nanoparticles were characterised by using scanning electron microscopy, X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy and zeta potential reader. The Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles had spherical structures with diameters in the range of 198–201 nm. Further, MSPE was performed by dispersion of Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles in a buffered aqueous solution accompanied by sonication. Next, the sorbents were accumulated by applying an external magnetic field and were washed with 4-(2-pyridylazo) resorcinol-dimethyl sulfoxide solution, for the purpose of desorbing the analyte. The extraction conditions (sample pH, washing and elution solutions, amount of sorbents, time of extraction, sample volume and effect of diverse ions), as well as Zineb-PAR first-order derivative spectra, were also evaluated. The calibration curve of the method was linear in the concentration range of 0.055–24.3 mg L^?1 with a correlation coefficient of 0.991. The limit of detection and limit of quantification values were 0.022 and 0.055 mg L^?1, respectively. The precision of the method for 0.27 mg L^?1 solution of the analyte was found to be less than 3.2%. The recoveries of three different concentrations (0.27, 1.37 and 13.7 mg L^?1) obtained 98.3%, 98.5% and 96.0%, respectively. The proposed Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles were found to have the capability of reusing for 7.0 times.     

Optimization of parameters for the alcoholic-assisted dispersive liquid–liquid microextraction of estrogens in water

Extraction and determination of estrogens in water samples were performed using alcoholic-assisted dispersive liquid–liquid microextraction (AA-DLLME) and high-performance liquid chromatography (UV/Vis detection). A Plackett–Burman design and a central composite design were applied to evaluate the AA-DLLME procedure. The effect of six parameters on extraction efficiency was investigated. The factors studied were volume of extraction and dispersive solvents, extraction time, pH, amount of salt and agitation rate. According to Plackett–Burman design results, the effective parameters were volume of extraction solvent and pH. Next, a central composite design was applied to obtain optimal condition. The optimized conditions were obtained at 220 μL 1-octanol as extraction solvent, 700 μL ethanol as dispersive solvent, pH 6 and 200 μL sample volume. Linearity was observed in the range of 1–500 μg L^?1 for E2 and 0.1–100 μg L^?1 for E1. Limits of detection were 0.1 μg L^?1 for E2 and 0.01 μg L^?1 for E1. The enrichment factors and extraction recoveries were 42.2, 46.4 and 80.4, 86.7, respectively. The relative standard deviations for determination of estrogens in water were in the range of 3.9–7.2 % (n = 3). The developed method was successfully applied for the determination of estrogens in environmental water samples.