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In this study, the one-step switchable hydrophilic solvent (SHS)-based effervescence tablet microextraction (ETME) was coupled with smartphone digital image colorimetry (SDIC) for the field detection of nickel ion (Ni2+) for the first time. Both extractant and CO2 were generated in situ when the novel SHS-based effervescence tablet was placed in the sample solution. The complexant 1-(2-pyridinylazo)-2-naphthaleno (PAN) dissolved from the effervescence tablet to form a stable complex with Ni2+, and the extractant was uniformly dispersed in the sample solution under the action of CO2 and fully in contact with Ni-PAN, which enabled efficient extraction of Ni2+. The color changes of the extraction phase were captured by smartphone, then a quantitative relationship between the concentrations of Ni2+ and color intensity of images captured using a smartphone was established by customized applet WASDIC, which realized quantitative analysis of Ni2+ in different samples. Under optimal conditions, the enhancement factor (EF) of the proposed method was 65.1, the limit of detection (LOD) and limit of quantification (LOQ) were 1.69 and 5.64 µg L-1, respectively. The developed method was successfully applied to the detection of trace Ni2+ in the environmental samples and natural medicines. And the applicability of the method for use in field analysis was validated.

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The aim of the current study was to separate and determine arsenic in water and fish samples using a novel and green solidified floating organic drop microextraction (SFODME), which is based on switchable hydrophilicity solvent (SHS)-assisted procedure followed by hydride generation atomic absorption spectrometry (HG-AAS). The 4-((2-hydroxyquinoline-7-yl)diazenyl)-N-(4-methylisoxazol-3-yl)benzene sulfonamide (HDNMBA) and tertiary amine (4-(2-aminoethyl)-N,N-dimethylbenzylamine (AADMBA) were used as ligand and SHS, respectively. The use of SHS promotes quantitative extraction of arsenic complexes into an extraction solvent (1-undecanol). Some factors that impact extraction recovery were studied. Under optimal conditions, the limit of detection (LOD) and limit of quantification (LOQ) were 0.005 µg L-1 and 0.015 µg L-1, respectively. The calibration graph was linear up to 900.0 µg L-1 arsenic, with the enrichment factor is 267. The proposed SHS-SFODME methodology for arsenic quantification in water and fish samples was successfully implemented. The environmental friendliness and safety of proposed method were approved by the Analytical Greenness Calculator (AGREE) and the Blue Applicability Grade Index (BAGI) tools.

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Synthetic cannabinoids are still a growing trend among drug users and consist of a group of hundreds of highly potent compounds. To investigate the use of such substances, sample preparation of biological matrices is a crucial step prior to instrumental analysis. Although different efficient extraction techniques have been proposed for that aim, they usually do not fit eco-friendly guidelines that have been gaining popularity in recent years, such as Green Analytical Toxicology. This work uses describes for the first time the use of switchable hydrophilicity solvent-based homogenous liquid-liquid microextraction (SHS-HLLME) for synthetic cannabinoids. This is a green technique that replaces highly toxic organic reagents for switchable hydrophilicity solvents (SHS), substances that can be either water-miscible or immiscible depending on their protonation. Thus, by simply adjusting the pH of the system, these SHS can be used as extraction solvents. A full optimization study including type of SHS, volume of protonated SHS, volume of NaOH, salting-out effect, and extraction time was performed. The optimized procedure consisted of precipitating the proteins of 300 µL of plasma with 300 µL of acetonitrile followed by centrifugation; evaporation of the organic solvent under N2 stream; addition of 500 µL of the protonated DPA, DPA-HCl (6 M) (1:1, v/v); addition of 500 µL of NaOH (10 M); and finally centrifugation and evaporation. Validation results showed determination coefficients ≥ 0.99 for the 0.1-10 ng/mL linear range; 0.01-0.08 ng/mL as limit of detection; 0.1 ng/mL as limit of quantitation; accuracy and imprecision were within acceptable ranges; matrix effect, recovery, and process efficiency ranged from -55.6 to 185.9%, 36-56.7%, and 18.5-148.4%, respectively. The SHS-HLLME herein described was fully optimized providing satisfactory recoveries of 31 synthetic cannabinoids at low concentrations requiring only 300 µL of plasma. In addition, the validation results showed that the technique is a reliable eco-friendly alternative for clinical and toxicological analysis.

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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%.

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The main purpose of this research article is to develop a vortex-assisted switchable hydrophilicity solvent liquid phase microextraction (VA-SHS-LPME) for the selective and efficient extraction of trace vanillin in food samples. Four switchable hydrophilicity solvents (SHSs) were prepared and tested for the extraction of vanillin. The obtained extract phase after phase separation was analyzed by UV-vis spectrophotometry. The extraction parameters including pH, vortex time, NaOH volume, and SHS volume were optimized using central composite design based on response surface methodology. Under optimized conditions, the linear range (0.2-400 ng mL-1 with r2 = 0.9985), limit of detection (0.06 ng mL-1), limit of quantitation (2.0 ng mL-1), extraction recovery (97 ± 4 %) and enhancement factor (220) were obtained. Also, relative standard deviations were less than 2.1 % indicating good precision. The VA-SHS-LPME procedure showed some advantages including good extraction, low consumption of chemical and low matrix effect. Finally, the VA-SHS-LPME procedure was applied for the determination of vanillin in food samples, and acceptable recoveries (91 ± 3-99 ± 3 %) were obtained.

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In this research, a green, selective and inexpensive switchable hydrophilicity solvent-based liquid phase microextraction (SHS-LPME) procedure has been optimized for the extraction and preconcentration of sulfadiazine (SDZ) in milk, honey and water samples prior to spectrophotometric analysis. Five variables affecting the SHS-LPME procedure were optimized using chemometric-based central composite design. For the SHS-LPME procedure, analytical parameters such as linearity, limit of detection, extraction recovery and enrichment factor were 15-300 µg L-1, 4.5 µg L-1, 96 ± 3% and 113, respectively. The precision of the method was investigated by repeatability and reproducibility studies. The relative standard deviation from these studies was found in the range of 2.4-4.5%. The recovery of the SDZ in the samples was in the range of 94 ± 4-99 ± 2%. Collected samples were analyzed by both the SHS-LPME procedure and the reference method using flow injection-flame atomic absorption technique, and the results were compared. There was no statistically significant difference between the two methods. This showed that the SHS-LPME procedure can be safely applied to the analysis of real samples.

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An on-line system employing switchable-hydrophilicity solvent-based liquid-phase microextraction (SHS-LPME) is described in this work. The method is based on the preconcentration of the species formed between cobalt and the reagent 1-nitroso-2-naphthol (NN), with subsequent detection by digital image colorimetry. The system's operation begins with the on-line mixture of sample, switchable solvent, and an alkaline agent in a reaction coil. Then the mixture is transported to an extraction chamber. The introduction of a proton donor leads to the passage of the solvent to its hydrophobic form, which allows phase separation. The rich phase is then directed to a glass tube, where detection is performed. Octanoic acid, sodium carbonate, and sulfuric acid were used as the extraction solvent, the alkaline agent, and the proton donor, respectively. Under optimized conditions, the method presented a detection limit of 0.8 µg L-1 and an enrichment factor of 41. The precision obtained was 4.8% (20 µg L-1). The accuracy of the method was tested by the analysis of Tomato Leaves certified reference material (NIST 1573a). The method was applied to the determination of cobalt in food, dietary supplements, and water samples. The method is presented as a green alternative and very accessible to the determination of cobalt in the analyzed samples.

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A salting-out-assisted switchable hydrophilicity solvent-based liquid phase microextraction (SA-SHS-LPME) was developed for the separation and determination of trace amounts of imatinib and N-desmethyl imatinib in biological and environmental samples by HPLC-UV. Triethylamine as a hydrophobic compound and protonated triethylamine carbonate as a hydrophilic one were switched by the addition or elimination of CO2 . The use of NaOH resulted in the elimination of CO2 from the sample solution, which led to the conversion of P-TEA-C into triethylamine (TEA) and as a result, the analytes was extracted and entered the TEA phase. The salting out was performed to speed up the formation of the TEA in the shape of fine droplets in the specimen solution. Furthermore, the impact of several momentous factors that influence the recovery of the extraction was investigated. Under the optimum conditions, the limit of detection and limit of quantification were obtained in ranges of 0.03-0.05 and 0.1-0.15 µg L-1 for imatinib and 0.04-0.06 and 0.13-0.20 µg L-1 for N-desmethyl imatinib, respectively. The preconcentration factor was 250. Inter- and intraday precision (RSD, n = 5) was <5%. In the case of imatinib and N-desmethyl imatinib in biological and environmental specimens, a range of 97.0-102% was obtained as the recovery.

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Herein, a sensitive and green method combining dispersive micro-solid phase extraction (D-µ-SPE) and homogeneous liquid-liquid microextraction (HLLME) has been developed. Magnetic layered double hydroxide nanoparticals were prepared and used as adsorbents in d-µ-SPE. The fascinating dissolvable characteristic of the material can eliminate elution step without usage of toxic organic solvents. Dipropylamine was used as a pH-triggered switchable hydrophilicity solvent that can change the miscible/immiscible states reversibly, achieving fast two-phase separation. To demonstrate the applicability of proposed method, three non-steroidal anti-inflammatory drugs including ketoprofen, naproxen and tolmetin in water samples were enriched and purified prior to HPLC-UV analysis. The influencing parameters such as pH of sample solution, amount of sorbent, vortex time, type and volume of acidic solution and SHS, volume of NaOH were optimized in detail. The method exhibits good linearity (0.1-50 ng/mL), low limits of detection (0.02-0.05 ng/mL), high precision (RSDs<9.3%) and acceptable accuracy (97.2%-105.7%). Therefore, the presented procedure is fast, sensitive, simple and suitable for determination of non-steroidal anti-inflammatory drugs from aqueous matrices.

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This work presents a sensitive and rapid analytical method for the determination of oxcarbazepine in human plasma and urine samples. A vortex-assisted switchable hydrophilicity solvent-based liquid phase microextraction (VA-SHS-LPME) was used to preconcentrate oxcarbazepine from the samples before the determination by gas chromatography mass spectrometry. The switchable hydrophilicity solvent was synthesized by protonating N,N-dimethylbenzylamine with carbon dioxide to make it totally miscible with an equivalent volume of water. Parameters of the VA-SHS-LPME method including volume of switchable hydrophilicity solvent, concentration/volume of sodium hydroxide and vortex period were systematically optimized. Under the optimum conditions, good linearity ranging from 27.03 to 353.47 µg/kg was obtained for the analyte. Limit of detection and quantitation values were found to be 6.2 and 21 µg/kg (mass base), respectively. The relative standard deviation was calculated as 6.9% for six replicate measurements of the lowest concentration of the calibration plot. Satisfactory recovery results were calculated in the range of 97-100% for human plasma and urine samples spiked at five different concentrations.

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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.

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A fully automated in-syringe switchable hydrophilicity solvent-based microextraction approach was suggested for the first time. Di-(2-ethylhexyl)phosphoric acid was investigated as a novel switchable hydrophilicity solvent. The microextraction procedure implemented into a syringe pump included dissociation of the extractant in alkaline sample solution resulting in homogeneous solution formation followed by in situ organic phase generation by acidification and its separation. The microextraction procedure was applied to the HPLC-UV determination of antimicrobial drugs (sulfamethoxazole and sulfamethazine) in human urine samples as a proof-of-concept example. The calibration graphs were linear over the concentration ranges of 0.06-50 mg L-1 for sulfamethoxazole and 0.13-50 mg L-1 for sulfamethazine. The LODs calculated from the blank tests based on 3σ were 0.02 and 0.04 mg L-1 for sulfamethoxazole and sulfamethazine, respectively. The sample throughput was 12 samples h-1. The possibility of using the proposed procedure for assessing sulfamethoxazole/sulfamethazine acetylation in metabolic processes by individual human phenotypes was shown.

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A novel microextraction method was developed by combining CO2-controlled switchable hydrophilicity solvent (SHS) with solidification of the aqueous phase (SAP), referred to as CSHS-SAP. It was applied for pre-concentration/extraction of the complexes of Pb-ammonium pyrrolidine dithiocarbamate (APDC) prior to GFAAS detection in raw bovine milk and milk products (whole-fat, half-skimmed and skimmed milks). In the CSHS-SAP microextraction, a clear interface was easily formed, and convenient and complete collection was achieved by directly transferring the SHS phase into a vial, which overcame the shortcomings of blurred interface and difficult collection of SHS phase using CSHS-based microextraction. SAP led to the increase of extraction recoveries for Pb2+ by 8-11%. Some important factors were optimised using a one-factor-at-a-time approach: 800 µL of N,N-dimethylbutylamine and water at a ratio of 1:1 as SHS, 1.0 g L-1 APDC as chelating agent, sample pH = 6.0, 0.6 mL of 1.0 mol L-1 NaOH, solidification time of 70 min and 300 µL of 0.5 mol L-1 HNO3 for back extraction. Under optimised conditions, limits of detection were as low as 0.01-0.02 µg kg-1 and enrichment factors reached more than 23-fold. Inter- and intra-day precisions had relative standard deviations of 3.6-6.4%. With the CSHS-SAP/GFAAS method Pb2+ was detected at 0.5-1.8 µg kg-1 in four bovine raw milk samples, which were collected from Hubei and Henan Provincial oil-producing area, China. However, Pb2+ was below the LOD in all of the local milk products. Overall, the newly developed CSHS-SAP/GFAAS method is convenient, efficient and robust, giving it great potential for rapid and accurate analysis of trace Pb2+ in liquid milks.

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A tertiary amine (N,N-dimethylcyclohexylamine, CyNMe2) was used as a switchable hydrophilicity solvent (SHS) for extracting phospholipids (PLs) from raw cream (RC), buttermilk (BM), concentrated buttermilk (CBM), and beta-serum (BS). The SHS extractions were performed with varying solvent-sample weight ratio at room temperature. The extracted PLs using CyNMe2 were recovered by bubbling CO2 at atmospheric pressure, switching the CyNMe2 into its respective salt. For comparison, the PLs were also extracted using Folch (FE) and Mojonnier (ME) extraction. The extraction efficiency of SHS varied from 0.33% to 99%, depending on the type of byproduct. The SHS extracted up to 99% of the PLs directly from BM, while only 11.37% ± 0.57% and 2.66% ± 0.56% of the PLs were extracted with FE and ME, respectively. These results demonstrate the applicability of SHS for the extraction of PLs from dairy byproducts.

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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%.

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A rapid and eco-friendly method was developed to extract and pre-concentrate sulfonamides (sulfadiazine, sulfamerazine and sulfadimethoxine) from chicken meat before high-performance liquid chromatographic analysis. The method involved rapid microwave-assisted extraction with hydrochloric acid (pH = 5), further solid phase purification using HLB cartridge and 5% ammonium hydroxide, and homogeneous liquid-liquid microextraction using hexanoic acid as switchable hydrophilicity solvent. The overall time required for sample preparation was 10 min and the volume of organic solvent used for extraction was only 200 µL. The method exhibited good linearity (r2 > 0.9941), low limits of detection (2.5-6.0 ng/g) and allowed quantification of target sulfonamides spiked at levels of 50-400 ng/g in chicken meat with spiked recoveries in the range of 94.1%-112.0%.

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First time we launch an innovative and simple portable in a closed micropipette tip switchable hydrophilicity microextraction syringe system (µS-SHS) couple with electrothermal atomic absorption spectroscopy (ETAAS) was developed for preconcentration and determination of vanadium using 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol (5- Br-PADAP), as complexing. In the proposed method decanoic acid was used as a switchable hydrophilicity extraction solvent and their polarity was switched on and off (water miscible/immiscible) by simply changing their pH. The phase separation was induced by simply adding sulfuric acid that switch off hydrophilicity (nondispersed/immiscible) of decanoic acid. The metal complex enriched phase (V-(5-Br-PADAP-SHS) was separated by simply removing the aqueous phase through manually dispensed syringe system. Then finally acidic ethanol drawn into the syringe contains metal complex enriched SHS phase to reduce viscosity and directly injected into the ETAAS by using an enclosed micropipette tip syringe system. The multivariate strategy was applied to screen out and optimized the variables. Limit of detection (LOD), enhancement factor (EF) and relative standard deviation (RSD) were found 0.0075 µg L-1, 120 and 2.91%, respectively. Certified reference material of riverine water (SLRS-4), Apple leaves (NIST SRM 1515) and a standard addition method was used to validate the present method. Developed method was applied to water and food samples. We successfully applied the proposed method to analyze vanadium in different real food and water samples.

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A simple and efficient method combining solid-phase extraction (SPE) with homogeneous liquid-liquid microextraction (HLLME) has been developed for fast pretreatment of chloramphenicol (CAP) from water samples prior to determination by high-performance liquid chromatography-ultraviolet detection. Oasis HLB sorbent was chosen for SPE. In HLLME, N,N-dimethylcyclohexylamine was used as a CO2-triggered switchable solvent that could switch reversibly between hydrophilic and hydrophobic forms. The parameters influencing both SPE and HLLME were investigated and optimized. Under the optimal conditions, the method exhibited low limit of detection (0.1 ng/mL), good linearity (0.5-50 ng/mL), acceptable precision (RSD <5.0%) and accuracy (RE <4.0%). An enrichment factor of 340 was obtained. The proposed method is simple, fast, cost-effective, and suitable for the determination of trace chloramphenicol in water matrices. Graphical abstract ᅟ.

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A simple, fast, and sensitive method was developed for the determination of diclazepam in urine using a solvent with switchable hydrophilicity in liquid-liquid microextraction followed by gas chromatography-mass spectrometry. N,N-Dimethylcyclohexylamine was used as the extraction solvent with switchable hydrophilicity, because it can be made miscible or immiscible with aqueous phase by adding hydrochloric acid and sodium hydroxide. Experimental parameters affecting the extraction efficiency, such as the volume of hydrochloric acid, the type and volume of the solvent with switchable hydrophilicity, the volume of sodium hydroxide, and the extraction time, were investigated. Under the optimal conditions, the intraday and interday recoveries ranged from 76.5% to 90.3% with relative standard deviations between 3.3% and 6.5% (n=6). The linear range was found to be 0.025-2.5 mg/L, with r2 greater than 0.99 and limit of detection of 0.007 mg/L. This method provided excellent linearity, precision, and recovery, and thus, can be applied to the analysis of diclazepam in urine due to its simplicity, accuracy, and practicality.

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In this study, a new method based on homogeneous liquid-phase microextraction was developed for the determination of methamphetamine (MA) in urine samples. Dipropylamine (DPA), as a solvent with switchable hydrophilicity, was used as the extraction solvent and can be miscible/immiscible based on variable pH values of the aqueous sample solution. The effects of operational extraction parameters such as DPA volume, temperature, the amount of added acid and base solutions, and NaCl content of the sample were investigated. Under optimal conditions the preconcentration factor, limit of detection and linearity of the method were achieved in the ranges of 98.8, 1.5 µgL-1 and 5-1500 µgL-1, respectively. Also, within-run precision, between-run precision and robustness of the method were investigated. Finally, the proposed method was successfully applied to the analysis of MA in urine sample.

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