Switchable-hydrophilicity solvent liquid-liquid microextraction versus dispersive liquid-liquid microextraction prior to HPLC-UV for the determination and isolation of piperine from Piper nigrum L.

Switchable-hydrophilicity solvent liquid-liquid microextraction and dispersive liquid-liquid microextraction were compared for the extraction of piperine from Piper nigrum L. prior to its analysis by using high-performance liquid chromatography with UV detection. Under optimum conditions, limits of detection and quantitation were found as 0.2-0.6 and 0.7-2.0 µg/mg with the two methods, respectively. Calibration graphs showed good linearity with coefficients of determination (R2 ) higher than 0.9962 and percentage relative standard deviations lower than 6.8%. Both methods were efficiently used for the extraction of piperine from black and white pepper samples from different origins and percentage relative recoveries ranged between 90.0 and 106.0%. The results showed that switchable-hydrophilicity solvent liquid-liquid microextraction is a better alternative to dispersive liquid-liquid microextraction for the routine analysis of piperine in food samples. A novel scaled-up dispersive liquid-liquid microextraction method was also proposed for the isolation of piperine providing a yield of 102.9 ± 4.9% and purity higher than 98.0% as revealed by NMR spectroscopy.

Edible oil-based switchable-hydrophilicity solvent liquid-liquid microextraction prior to smartphone digital image colorimetry for the determination of total curcuminoids in food samples.

Edible oil-based switchable-hydrophilicity solvent liquid-liquid microextraction was coupled with smartphone digital image colorimetry for the determination of total curcuminoids. Images of the colored extracts were captured in a laboratory-made colorimetric box, which were then split into their red-green-blue channels. Optimum extraction conditions were achieved using 550 µL of almond oil as the extraction solvent and 0.40 M sodium hydroxide for hydrolysis of the oil to the salt of its fatty acid. Phosphoric acid (2.0 mL, 4.0 M) was used as the hydrophilicity-switching trigger, while pH of the sample solution adjusted to 5.50 and extraction time of 1.0 min, were found to be optimum. Optimum detection conditions were achieved at a distance of 7.0 cm from the detection camera, a region of interest of 175 px2, a detection wavelength of 420 nm and 50.0% brightness of the light source. The limit of detection was found to be 0.020 µg mL-1. A good linearity was achieved as indicated by coefficients of determination above 0.9965. The proposed method was used for the determination of total curcuminoids in tea and turmeric samples with percentage relative recoveries of 95.0-105.0% and percentage relative standard deviations below 8.7%.

Dispersive liquid-liquid microextraction based on solidification of floating organic drop combined with field-amplified sample injection in capillary electrophoresis for the determination of beta(2)-agonists in bovine urine.

Dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) was for the first time combined with field-amplified sample injection (FASI) in CE to determine four ß(2)-agonists (cimbuterol, clenbuterol, mabuterol, and mapenterol) in bovine urine. Optimum BGE consisted of 20 mM borate buffer and 0.1 mM SDS. Using salting-out extraction, ß(2)-agonists were extracted into ACN that was then used as the disperser solvent in DLLME-SFO. Optimum DLLME-SFO conditions were: 1.0 mL ACN, 50 µL 1-undecanol (extraction solvent), total extraction time 1.5 min, no salt addition. Back extraction into an aqueous solution (pH 2.0) facilitated direct injection of ß(2)-agonists into CE. Compared to conventional CZE, DLLME-SFO-FASI-CE achieved sensitivity enhancement factors of 41-1046 resulting in LODs in the range of 1.80-37.0 µg L(-1). Linear dynamic ranges of 0.15-10.0 mg L(-1) for cimbuterol and 15-1000 µg L(-1) for the other analytes were obtained with coefficients of determination (R(2)) ≥ 0.9901 and RSD% ≤5.5 (n = 5). Finally, the applicability of the proposed method was successfully confirmed by determination of the four ß(2)-agonists in spiked bovine urine samples and accuracy higher than 96.0% was obtained.

Switchable-hydrophilicity solvent liquid-liquid microextraction combined with smartphone digital image colorimetry for the determination of palladium in catalytic converters.

Switchable-hydrophilicity solvent liquid-liquid microextraction was coupled with smartphone digital image colorimetry for the determination of palladium as its metal chelate with N,N-diethyl-N'-benzoylthiourea. Images of the colored extract were captured in a homemade colorimetric box, which were split into their red-green-blue channels. The blue channel was used to determine the concentration of palladium. Optimum extraction conditions were achieved using 600 µL of triethylamine as the extraction solvent and 4.0 mL of 10 M sodium hydroxide as the hydrophilicity-switching trigger within 1.0 min extraction time. Optimum complexation conditions were obtained at a sample pH of 4.50, and metal/ligand mole ratio of 1:2 within 3.0 min. Optimum detection conditions were achieved at a distance of 7.0 cm between the sample solution and the detection camera, a region of interest of 175.0 px2 at a detection wavelength of 480.0 nm and 30.0% brightness of the monochromatic light source. Limits of detection and quantitation were found to be less than 0.7 and 1.8 µg g-1, respectively. A good linearity with coefficients of determination above 0.9974 was obtained. Accuracy was checked via a single-factor analysis of variance (ANOVA) test by comparing the results with the ones obtained using flame-atomic absorption spectrometry and the results were statistically in a good agreement (P > 0.05). The proposed method was applied for the determination of palladium in catalytic converters with percentage relative recoveries ranging between 95.7 and 103.7% and percentage relative standard deviations below 4.0%.

Smartphone digital image colorimetry combined with dispersive solid-phase microextraction for the determination of boron in food samples.

Simple, inexpensive and accurate analytical methods are in high demand. Dispersive solid-phase microextraction (DSPME) was used in combination with smartphone digital image colorimetry (SDIC) to determine boron in nuts as an approach replacing existing costly alternatives. A colorimetric box was designed to capture images of standards and sample solutions. ImageJ software was used to link pixel intensity to the analyte concentration. Under optimum extraction and detection conditions, linear calibration graphs were obtained with coefficients of determination (R2) above 0.9955. Percentage relative standard deviations (%RSD) were below 6.8 %. The limits of detection (LOD) ranged between 0.07 and 0.11 µg mL-1 (1.8 to 2.8 µg g-1), which were sufficient for detection of boron in nut samples (i.e., almond, ivory, peanut and walnut), with percentage relative recoveries (%RR) between 92.0 and 106.0 %.

Ultrasound-assisted emulsification microextraction for the determination of ephedrines in human urine by capillary electrophoresis with direct injection. Comparison with dispersive liquid-liquid microextraction.

Ultrasound-assisted emulsification microextraction and dispersive liquid-liquid microextraction were compared for extraction of ephedrine, norephedrine, and pseudoephedrine from human urine samples prior to their determination by capillary electrophoresis. Formation of a microemulsion of the organic extract with an aqueous solution (at pH 3.2) containing 10% methanol facilitated the direct injection of the final extract into the capillary. Influential parameters affecting extraction efficiency were systematically studied and optimized. In order to enhance the sensitivity further, field-amplified sample injection was applied. Under optimum extraction and stacking conditions, enrichment factors of up to 140 and 1750 as compared to conventional capillary zone electrophoresis were obtained resulting in limits of detection of 12-33 µg/L and 1.0-2.8 µg/L with dispersive liquid-liquid microextraction and ultrasound-assisted emulsification microextraction when combined with field-amplified sample injection. Calibration graphs showed good linearity for urine samples by both methods with coefficients of determination higher than 0.9973 and percent relative standard deviations of the analyses in the range of 3.4-8.2% for (n = 5). The results showed that the use of ultrasound to assist microextraction provided higher extraction efficiencies than disperser solvents, regarding the hydrophilic nature of the investigated analytes.

Magnetic Nanoparticle-Based Dispersive Solid-Phase Microextraction of Three UV Blockers Prior to Their Determination by HPLC-DAD.

The need for proper handling of environmental samples is significant, owing to their environmental effects on both humans and animals, as well as their immediate surroundings. In the current study, magnetic nanoparticle-based dispersive solid-phase microextraction was combined with high-performance liquid chromatography using a diode array as the detector (HPLC-DAD) for both the separation and determination of three different UV blockers, namely octocrylene, ethylhexyl methoxycinnamate, and avobenzone. The optimum conditions for the extraction were found to be as follows: Stearic acid magnetic nanoparticles (20 mg) as the sorbent, acetonitrile (100 µL) as the eluent, as well as a sample pH of 2.50, adsorption and desorption time of 1.0 min, with a 3.0 mL sample volume. The limits of detection were as low as 0.05 µg mL-1. The coefficient of determination (R2) was above 0.9950, while the percentages of relative recoveries (%RR) were between 81.2 and 112% for the three UV blockers from the environmental water samples and sunscreen products.

Smartphone Digital Image Colorimetry for the Determination of Aluminum in Antiperspirant Products.

Objectives: This study aims to present a method for the determination of the aluminum in antiperspirant products (APPs) by chelating it with quercetin before its detection by smartphone digital image colorimetry (SDIC). Materials and Methods: Samples were prepared by closed-vessel acid digestion in PTFE cups. This was followed by complexation of aluminum in the sample solution using quercetin as a chelating agent. Sample solutions were transferred into a quartz ultraviolet/visible detection microcuvette for detection in a homemade colorimetric box designed for capturing images of the yellow complex with a smartphone camera. The pixel intensity of the images was converted to numbers for quantitation using ImageJ software for a personal computer. An independent study using high-performance liquid chromatography-diode-array detection was conducted to check the accuracy of the proposed method. Results: Optimum SDIC conditions included a Samsung C9 smartphone as the detection camera, a cropped region of interest of 6400 px2, and the side position of the colorimetric box were selected for capturing the images of the sample solutions placed 10.0 cm from the detection camera, whereas optimum complexation conditions were found to be as sample pH of 5.5, sample volume of 3.0 mL, complexation time of 1.0 min and a ligand concentration of 0.28 mmol L-1. Analytical performance of the method included a limit of detection of 0.5 µmol L-1 and a coefficient of determination (R2) of the calibration graph of 0.9981. Conclusion: The proposed method was successfully applied for the determination of aluminum in APPs with percentage recoveries ranging from 80.0 to 109.6%.

Evaluation of low-to-moderate arsenic exposure, metabolism and skin lesions in a Turkish rural population exposed through drinking water.

BACKGROUND: There is no human data regarding the exposure, metabolism and potential health effects of arsenic (As) contamination in drinking water in the Central Anatolian region of Turkey. METHODS: Residents in ten villages with drinking water of total As (T-As) level >50 µg L-1 and 10-50 µg L-1 were selected as an exposed group (n = 420) and <10 µg L-1 as an unexposed group (n = 185). Time-weighted average-As (TWA-As) intake was calculated from T-As analysis of drinking water samples. Concentrations of T-As in urine and hair samples, urinary As species [i.e., As(III), As(V), MMA(V) and DMA(V], and some micronutrients in serum samples of residents of the study area were determined. Primary and secondary methylation indices (PMI and SMI, respectively) were assessed from urinary As species concentrations and the presence of skin lesion was examined. RESULTS: TWA-As intake was found as 75 µg L-1 in the exposed group. Urinary and hair T-As and urinary As species concentrations were significantly higher in the exposed group (P < 0.05). The PMI and SMI values revealed that methylation capacities of the residents were efficient and that there was no saturation in As metabolism. No significant increase was observed in the frequency of skin lesions (hyperpigmentation, hypopigmentation, keratosis) of the exposed group (P > 0.05). Only frequency of keratosis either at the hand or foot was higher in individuals with hair As concentration >1 µg g-1 (P < 0.05). CONCLUSIONS: Individuals living in the study area were chronically exposed to low-to-moderate As due to geological contamination in drinking water. No significant increase was observed in the frequency of skin lesions. Because of the controversy surrounding the health risks of low-to-moderate As exposure, it is critical to initiate long-term follow-up studies on health effects in this region.

Smartphone digital image colorimetry combined with solidification of floating organic drop-dispersive liquid-liquid microextraction for the determination of iodate in table salt.

Smartphone digital image colorimetry (SDIC), combined with solidification of floating organic drop-dispersive liquid-liquid microextraction (SFOD-DLLME), was proposed for the determination of iodate ions. A colorimetric box was designed to capture images of sample solutions. Factors affecting the efficiency of SDIC included type of phone, region of interest, position of camera, and distance between camera and sample solution. Optimum SFOD-DLLME conditions were achieved with 1-undecanol (500 µL) as the extraction solvent, ethanol (1.5 mL) as the disperser solvent within 20 s extraction time. Limit of detection (LOD) was found as 0.1 µM (0.2 µg g-1) and enrichment factors ranged between 17.4 and 25.0. Calibration graphs showed good linearity with coefficients of determination higher than 0.9954 and relative standard deviations lower than 5.6%. The proposed method was efficiently applied to determine iodate in table salt samples with percentage relative recoveries ranging between 89.3 and 109.3%.

Dispersive liquid-liquid microextraction for the isolation and HPLC-DAD determination of three major capsaicinoids in Capsicum annuum L.

Dispersive liquid-liquid microextraction (DLLME) was combined with high-performance liquid chromatography-diode-array detector (HPLC-DAD) for the extraction and quantitation of three major capsaicinoids (i.e. capsaicin, dihydrocapsaicin and nordihydrocapsaicin) from pepper (Capsicum annuum L.). Chloroform (extraction solvent, 100 µL), acetonitrile (disperser solvent, 1250 µL) and 30 s extraction time were found optimum. The analytes were back-extracted into 300 µL of 50 mM sodium hydroxide/ methanol, 45/55% (v/v), within 15 s before being injected into the instrument. Enrichment factors ranged from 3.3 to 14.7 and limits of detection from 5.0 to 15.0 µg g-1. Coefficients of determination (R2) and %RSD were higher than 0.9962 and lower than 7.5%, respectively. The proposed method was efficiently applied for the extraction and quantitation of the three capsaicinoids in six cultivars of Capsicum annuum L. with percentage relative recoveries in the range of 92.0%-108.0%. DLLME was also scaled up for the isolation of the three major capsaicinoids providing purity greater than 98.0% as confirmed by liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance (NMR) analysis, which significantly reduced the extraction time and organic solvent consumption.

Switchable-hydrophilicity solvent liquid-liquid microextraction prior to magnetic nanoparticle-based dispersive solid-phase microextraction for spectrophotometric determination of erythrosine in food and other samples.

A combination of switchable-hydrophilicity liquid-liquid microextraction prior to magnetic nanoparticle-based dispersive solid-phase microextraction is proposed for the determination of erythrosine using UV/Vis spectrophotometry at 520 nm. Under optimum conditions (i.e., 1.0 mL octylamine as the extraction solvent, 1.5 mL of 10.0 M sodium hydroxide as the phase separation trigger, pH 4.0, 750 µL of acetone as the eluent, 10.0 mg of Fe3O4@XAD-16 as the adsorbent, and 15.0 mL of the sample solution), the method showed a superior analytical performance with limits of detection less than 25.9 ng mL-1, limits of quantitation less than 86.3 ng mL-1 and linear dynamic ranges ranging between 86.3 and 1000 ng mL-1. Percentage relative standard deviations were less than 4.1 and 7.2% for intra-day and inter-day, respectively. The method was successfully applied for the extraction and determination of erythrosine in food samples and other consumer products with recoveries in the range of 94.6-103.9% and within extraction time of 7.8 min per sample.

Switchable-hydrophilicity solvent liquid-liquid microextraction of non-steroidal anti-inflammatory drugs from biological fluids prior to HPLC-DAD determination.

Switchable-hydrophilicity solvent liquid-liquid microextraction was used prior to high-performance liquid chromatography with diode-array detector (HPLC-DAD) for the determination of four non-steroidal anti-inflammatory drugs [i.e., ketoprofen, etodolac, flurbiprofen and ibuprofen] in human urine, saliva and milk. Optimum extraction conditions were as follows: 500 µL switched-on N,N-dimethylcyclohexylamine as the extraction solvent, 9.5 mL of the aqueous phase, 500 µL 20 M sodium hydroxide as a switching-off trigger, and within 30 s extraction time. A portion of the final extract was directly injected into HPLC. Under optimized extraction and chromatographic conditions, limits of detection ranged between 0.04 and 0.18 µg mL-1 in all matrices analyzed. Good linearity with coefficients of determination (R2) ranging between 0.9955 and 0.9998, and percentage relative standard deviations (%RSD) of 0.9-7.7% were obtained. The proposed method was efficiently used for the extraction of the analytes in the biological fluids with percentage relative recoveries (%RR) ranging between 95.7 and 109.2%.

Determination of antazoline and tetrahydrozoline in ophthalmic solutions by capillary electrophoresis and stability-indicating HPLC methods.

Capillary electrophoretic (CE) and high performance liquid chromatographic (HPLC) methods were developed and optimized for the determination of antazoline (ANT) and tetrahydrozoline (TET) in ophthalmic formulations. Optimum electrophoretic conditions were achieved using a background electrolyte of 20mM phosphate buffer at pH 7.0, a capillary temperature of 25°C, a separation voltage of 22 kV and a pressure injection of the sample at 50 mbar for 17s. HPLC analysis was performed with Kinetex (150 × 4.6mm ID × 5 µm) (Phenomenex, USA) analytical column with 1 mL min(-1) flow rate of mobile phase which consisted of 0.05% TFA in bidistilled water (pH adjusted to 3.0 with 5M NaOH) and acetonitrile/buffer in the ratio of 63:37 (v/v) at room temperature. Injection volume of the samples was 10 µL and the wavelength of the detector was set at 215 nm for monitoring both analytes. Calibration graphs showed a good linearity with a coefficient of determination (R(2)) of at least 0.998 for both methods. Intraday and interday precision (expressed as RSD%) were lower than 2.8% for CE and 0.92% for HPLC. The developed methods were demonstrated to be simple and rapid for the determination of ANT and TET in ophthalmic solutions providing recoveries in the range between 97.9 and 102.70% for CE and HPLC.

Determination of parabens in human milk and other food samples by capillary electrophoresis after dispersive liquid-liquid microextraction with back-extraction.

Dispersive liquid-liquid microextraction (DLLME) with back-extraction was used prior to capillary electrophoresis (CE) for the extraction of four parabens. Optimum extraction conditions were: 200 µL chloroform (extraction solvent), 1.0 mL acetonitrile (disperser solvent) and 1 min extraction time. Back-extraction of parabens from chloroform into a 50mM sodium hydroxide solution within 10s facilitated their direct injection into CE. The analytes were separated at 12°C and 25 kV with a background electrolyte of 25 mM borate buffer containing 5.0% (v/v) acetonitrile. Enrichment factors were in the range of 4.3-10.7 and limits of detection ranged from 0.1 to 0.2 µg mL(-1). Calibration graphs showed good linearity with coefficients of determination (R(2)) higher than 0.9957 and relative standard deviations (%RSDs) lower than 3.5%. DLLME-CE was demonstrated to be a simple and rapid method for the determination of parabens in human milk and food with relative recoveries in the range of 86.7-103.3%.

Dispersive liquid-liquid microextraction combined with field-amplified sample stacking in capillary electrophoresis for the determination of non-steroidal anti-inflammatory drugs in milk and dairy products.

Dispersive liquid-liquid microextraction (DLLME) was coupled with field-amplified sample stacking in capillary electrophoresis (FASS) for the determination of five non-steroidal anti-inflammatory drugs (NSAIDs) in bovine milk and dairy products. After extraction, the enriched analytes were back-extracted into a basic aqueous solution for injection into CE. Under optimum conditions, enrichment factors were in the range 46-229. Limits of detection of the analytes ranged from 3.0 to 13.1 µg kg(-1) for all matrices analysed. Calibration graphs showed good linearity with coefficients of determination (R(2))≥ 0.9915 and relative standard deviations (RSD%) of the analyses in the range of 0.6-6.2% (n=5). Recoveries of all NSAIDs from bottled milk, raw milk, yogurt and white cheese samples were in the ranges of 86.6-109.3%, 84.3-100.5%, 77.4-107.3%, and 90.9-101.6%, respectively. DLLME-FASS-CE was demonstrated to be a rapid and convenient method for the determination of NSAIDs in milk and dairy products.