Dispersive Liquid-liquid Microextraction Procedure Research Articles

Implementation of multicriteria decision analysis in design of experiment for dispersive liquid-liquid microextraction optimization for chlorophenols determination

A novel and efficient approach to optimization of extraction step prior the chromatographic determination of nine chlorinated phenols is described. It is based on the combination of design of experiments and multicriteria decision analysis. Such an approach is used to optimize dispersive liquid-liquid microextraction procedure for the determination of 9 chlorophenols in water samples. Three parameters are optimized – sample volume, volume of disperser solvent and extraction solvent. Combination of the technique for order of preference by similarity to ideal solution with central composite design allows to perform multi-analyte procedure optimization. It gives information about the efficiency of the system for every experimental plan point in terms of closeness to ideal solution. The optimal conditions for extraction of chlorophenols are 76 μL of extraction solvent, 0.6 mL of dispersive solvent and 6.7 mL of water sample. The presented approach has the potential to be applied in variety of optimization systems.

Development of CO2-Mediated Switchable Hydrophilicity Solvent-Based Microextraction Combined with HPLC-UV for the Determination of Bisphenols in Foods and Drinks

In traditional dispersive liquid-liquid microextraction procedures, both extraction and dispersive solvents are required, and thus, it increases the consumption of organic solvent. Herein, we reported a CO2-mediated switchable hydrophilicity solvent-based microextraction (SHS-BME) for the determination of bisphenol compounds (BPCs) in complex milk and drink samples. N,N-Dimethylcyclohexylamine was used as a switchable hydrophilicity solvent; it can switch reversibly between one form that is miscible with water and another that forms a biphasic mixture with water, and thus allow extraction of the analytes in a homogeneous phase without dispersive solvent. Several important parameters were screened and optimized by single factor experiments and central composite design as follows: 782 μL of switchable solvent, 375 μL of NaOH solvent, and 1.1:1 switchable solvent/water (v/v). Under the optimized SHS-BME conditions, the limit of detections (LODs) for BPCs in milk, orange juice, and energy drink samples were in the range of 0.27–0.40 μg L−1 for BPE, 0.17–0.30 μg L−1 for BPA, and 0.50–0.67 μg L−1 for BPB, respectively, and the extraction recoveries for BPCs were in the range of 79.5–103.4% in milk, of 84.5–97.5% in orange juice, and of 91.9–101.2% in energy drinks. The precision of the method, based on relative standard deviations (RSDs), ranged from 1.7 to 4.8% and from 2.1 to 5.7% for intra-day and inter-day comparisons, respectively. In total, this SHS-BME method possesses many advantages, such as high extraction recovery and high detection sensitivity (low LODs and RSDs), no requirement of dispersive solvent, simple operational procedure, reducing the pretreatment time and workload, and so on. Therefore, it has a great potential application value for detection of trace BPCs in routine food tests.

Ultra-Trace Determination of Silver in Water, Soil and Radiology Film Samples Using Dispersive Liquid-Liquid Microextraction and Microvolume UV–Vis Spectrophotometry

In this research, a Dispersive Liquid-Liquid MicroExtraction (DLLME) method coupled to UV-vis spectrophotometry was developed for the indirect determination of silver ion. The method is based on the catalytic effect of the silver ion on the oxidation of congo red by potassium peroxodisulphate and extraction with DLLME procedure using chloroform (extraction solvent) containing cetyltrimethyl ammonium bromide which provides counter ion and also acts as a disperser. After extraction, the phase separation is performed with a centrifugation, and the silver ion is determined in the enriched phase by UV-Vis spectrophotometry. Several factors affecting the microextraction efficiency, such as pH of the solution, extraction time, type and volume of extraction solvent were investigated. Under optimum conditions, a linear calibration graph in the range of 0.5-105.0 ng/mL of silver ion in the initial solution with r2 = 0.9987 (n=10) was obtained. Detection limit of the method was 0.2 ng/mL and the Relative Standard Deviation (RSD) for 3 and 70 ng/mL of silver ion was 3.5 and 1.7 (n=10), respectively. The enrichment factor was 54. The method was successfully applied to the determination of trace amounts of Ag(I) in radiology film and environmental matrices.

Monitoring and health risk of mycotoxins in imported wines and beers consumed in Thailand

The presence of mycotoxins has been reported in a wide range of agricultural commodities including wine and beer. Due to the widespread consumption of these beverages, risk assessment of contamination by toxins is required for consumer health. In the present study, multi-residue analysis for the determination of mycotoxins was undertaken to survey the incidence of mycotoxins in imported wines and beers being commercialised in Thailand, and to assess the consumer health risk. Samples of red wines (100) and beers (100) were collected randomly from supermarkets and retail shops in Bangkok, Thailand and were extracted using the dispersive liquid-liquid micro-extraction procedure. The quantitation and confirmation of 19 mycotoxins were performed using liquid chromatography tandem-mass spectrometry with an electro-spray ionisation interface in the multiple-reaction monitoring mode. The results demonstrated that the wine and beer samples were contaminated with mycotoxins at 35 and 13%, respectively. The most prominent mycotoxins found in wines wereAlternaria toxins, ochratoxin A, and fumonisins, whereas zearalenone and deoxynivalenol were the most prevalent mycotoxins found in contaminated beers. However, ochratoxin A levels were far below the maximum limits established by the European Union. As indicated by the risk assessment, mycotoxin exposure via imported wines and beers were at safe levels in the Bangkok urban area.

Vortex-Assisted Modified Dispersive Liquid-Liquid Microextraction of Trace Levels of Cadmium in Surface Water and Groundwater Samples of Tharparkar, Pakistan, Optimized by Multivariate Technique.

A simple vortex-assisted modified dispersive liquid-liquid microextraction procedure is proposed for the enrichment of cadmium (Cd+2) in surface (stored rainwater) and groundwater of the Tharparkar district in Pakistan, before analysis by flame atomic absorption spectrometry. Ammonium pyrrolidinedithiocarbamate was used as a ligand to make a hydrophobic complex of Cd+2, which was extracted in an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate), and the nonionic surfactant Triton X-114 was applied as a dispersing medium. The contents of tubes were shaken for different time intervals on a vortex mixer to enhance extraction efficiency. A multivariate strategy was used to simultaneously evaluate seven factors including, concentration of the complexing reagent, pH, amounts of ionic liquid and Triton X-114, vortex shaking time, centrifugation time and extracting solution for their influence on the percentage recovery of the analyte. The important variables were further optimized by central composite design. The preconcentration factor and LOD were observed as 76.9 and 0.048 µg/L, respectively. The Certified Reference Material SRM1643e was used to check the validity of the developed method, and the RSD was found to be 4.02%. The proposed technique was successfully applied for the enrichment of Cd+2 in groundwater and surface water samples from the southeastern part of Pakistan. The observed results revealed that the concentration of Cd+2 in groundwater was higher than the World Health Organization recommended value of 3 µg/L for drinking water. For adults weighing approximately 60 kg, consumption of groundwater for drinking and other domestic purposes would provide levels of Cd+2 that are 2- to 3-fold higher than the provisional maximum tolerable daily intake.

Coupling dispersive liquid-liquid microextraction to inductively coupled plasma atomic emission spectrometry: An oxymoron?

Coupling dispersive liquid-liquid micro-extraction (DLLME) to inductively coupled plasma atomic emission spectrometry (ICP-AES) is usually troublesome due to the limited plasma tolerance to the organic solvents usually employed for metal extraction. This work explores different coupling strategies allowing the multi-element determination by ICP-AES of the solutions obtained after DLLME procedures. To this end, three of the most common extractant solvents in DLLME procedures (1-undecanol, 1-butyl-3-methyl-imidazolium hexafluorophosphate and chloroform) have been selected to face most of the main problems reported in DLLME-ICP-AES coupling (i.e., those arising from the high solvent viscosity and volatility). Results demonstrate that DLLME can be successfully coupled to ICP-AES after a careful optimization of the experimental conditions. Thus, elemental analysis in 1-undecanol and 1-butyl-3-methyl-imidazolium hexafluorophosphate extracts can be achieved by ICP-AES after a simple dilution step with methanol (1:0.5). Chloroform can be directly introduced into the plasma with minimum changes in the ICP-AES configuration usually employed when operating with aqueous solutions. Diluted inorganic acid solutions (1% w w−1 either nitric or hydrochloric acids) have been successfully tested for the first time as a carrier for the introduction of organic extractants in ICP-AES. The coupling strategies proposed have been successfully applied to the multi-element analysis (Al, Cu, Fe, Mn, Ni and Zn) of different water samples (i.e. marine, tap and river) by DLLME-ICP-AES.

Trace determination of five triazole fungicide residues in traditional Chinese medicine samples by dispersive solid-phase extraction combined with ultrasound-assisted dispersive liquid-liquid microextraction and UHPLC-MS/MS.

A novel and reliable method for determination of five triazole fungicide residues (triadimenol, tebuconazole, diniconazole, flutriafol, and hexaconazol) in traditional Chinese medicine samples was developed using dispersive solid-phase extraction combined with ultrasound-assisted dispersive liquid-liquid microextraction before ultra-high performance liquid chromatography with tandem mass spectrometry. The clean up of the extract was conducted using dispersive solid-phase extraction by directly adding sorbents into the extraction solution, followed by shaking and centrifugation. After that, a mixture of 400μL trichloromethane (extraction solvent) and 0.5mL of the above supernatant was injected rapidly into water for the dispersive liquid-liquid microextraction procedure. The factors affecting the extraction efficiency were optimized. Under the optimum conditions, the calibration curves showed good linearity in the range of 2.0-400 (tebuconazole, diniconazole, and hexaconazole) and 4.0-800ng/g (triadimenol and flutriafol) with the regression coefficients higher than 0.9958. The limit of detection and limit of quantification for the present method were 0.5-1.1 and 1.8-4.0ng/g, respectively. The recoveries of the target analytes ranged from 80.2 to 103.2%. The proposed method has been successfully applied to the analysis of five triazole fungicides in traditional Chinese medicine samples, and satisfactory results were obtained.

Determining heterocyclic aromatic amines in aqueous samples: A novel dispersive liquid-liquid micro-extraction method based on solidification of floating organic drop and ultrasound assisted back extraction followed by UPLC-MS/MS

A novel dispersive liquid-liquid microextraction based on solidification of floating organic droplet combined with ultrasound assisted back extraction for the determination of four heterocyclic aromatic amines in natural water samples prior ultra high-performance liquid chromatography-tandem mass spectrometry was developed. The analytes were extracted from the water samples by a dispersive liquid-liquid microextraction procedure based on solidification of floating organic drop, which was performed by a mixture composed by a less dense than water extraction solvent, 1-undecanol, and a dispersive solvent, methanol. After that, a novel ultrasound assisted back extraction step was performed in order to make the clean-up/enrichment procedure compatible with the detection requirements. Under optimum conditions, linearity ranged from 2.2 to 50ngmL−1, with enrichment factors from 130 to 136-folds. Thus limits of detection between 0.7 and 2.9ngmL−1 were obtained. Precision of the method was evaluated in terms of repeatability, relative standard deviations varied from 4.3% to 6.7%. Relative recoveries ranged from 92% to 106% for all analytes. The satisfactory performance demonstrated that the proposed methodology has a strong potential for application in the multi-residue analysis of heterocyclic aromatic amines present in complex environmental matrices.

Glyoxal and methylglyoxal as urinary markers of diabetes. Determination using a dispersive liquid–liquid microextraction procedure combined with gas chromatography–mass spectrometry

Glyoxal (GO) and methylglyoxal (MGO) are α-oxoaldehydes that can be used as urinary diabetes markers. In this study, their levels were measured using a sample preparation procedure based on salting-out assisted liquid–liquid extraction (SALLE) and dispersive liquid–liquid microextraction (DLLME) combined with gas chromatography-mass spectrometry (GC–MS). The effect of the derivatization reaction with 2,3-diaminonaphthalene, the addition of acetonitrile and sodium chloride to urine, and the DLLME step using the acetonitrile extract as dispersant solvent and carbon tetrachloride as extractant solvent were carefully optimized. Quantification was performed by the internal standard method, using 5-bromo-2-chloroanisole. The intraday and interday precisions were lower than 6%. Limits of detection were 0.12 and 0.06ngmL−1, and enrichment factors 140 and 130 for GO and MGO, respectively. The concentrations of these α-oxoaldehydes in urine were between 0.9 and 35.8ngg−1 levels (creatinine adjusted). A statistical comparison of the analyte contents of urine samples from non-diabetic and diabetic patients pointed to significant differences (P=0.046, 24 subjects investigated), particularly regarding MGO, which was higher in diabetic patients. The novelty of this study compared with previous procedures lies in the treatment of the urine sample by SALLE based on the addition of acetonitrile and sodium chloride to the urine. The DLLME procedure is performed with a sedimented drop of the extractant solvent, without a surfactant reagent, and using acetonitrile as dispersant solvent. Separation of the analytes was performed using GC–MS detection, being the analytes unequivocal identified. The proposed procedure is the first microextraction method applied to the analysis of urine samples from diabetic and non-diabetic patients that allows a clear differentiation between both groups using a simple analysis.

Determination of organotin compounds in sediment samples by dispersive liquid-liquid microextraction followed by gas chromatography – Pulsed flame photometric detection (DLLME-GC-PFPD)

Dispersive liquid-liquid microextraction (DLLME) was evaluated for the simultaneous determination of butyl-, phenyl- and octyltin compounds in sediment samples. The most significant factors in DLLME procedure were type and volume of extraction and disperser solvents, and the optimal conditions were reached when 413 and 34μL of methanol and tetrachloroethylene, respectively, were used. Under optimal conditions, the limit of detection and the relative standard deviation ranged between 0.3 and 1.0ngL−1 and 2–6%, respectively. The developed method was validated for the analysis of a certified reference material and spiked seawater and marine sediment samples, with satisfactory results. Finally, harbor sediment samples collected from the Chilean coastal region were analyzed to demonstrate the applicability of the developed method in the determination of organotin compounds in the environment.

New protocol based on high-volume sampling followed by DLLME-GC-IT/MS for determining PAHs at ultra-trace levels in surface water samples

Polycyclic Aromatic Hydrocarbons (PAHs), ubiquitous compounds coming from incomplete combustion processes, are very toxic species and can cause serious effects on the human health. At authors' knowledge, studies on PAHs levels in surface waters are scarce: the main problem regards the analytical implications due to analyzing such compounds at very low levels. This paper would like to present a new extraction protocol based on Dispersive Liquid-Liquid MicroExtraction (DLLME) procedure followed by GC-IT/MS for simultaneous determination of nine PAHs in surface water. Iso-octane is used as extraction solvent whereas no dispersive solvent is involved. An important issue regarded the procedure to obtain the emulsion without dispersive solvent but using ultrasounds; the other important novelty of this method of extraction regards the enrichment factors, that were demonstrated to be significantly high (up to 100,000). Methodological parameters such as the volume of surface water sample, the extraction solvent and relative volume, the time required for breaking emulsion and the salting-out effect have been investigated. Under the optimum experimental conditions (1L-volume of surface water sample, 300μL of isooctane as extraction solvent, 2min-ultrasound for the emulsion and 10minutes-agitation for breaking the emulsion, nitrogen stream for concentrating up to 10μL, analysis by GC-IT/MS) the method provides very good correlation coefficients (R2>0.99) in the range investigated, LODs and LOQs able to analyze such compounds in any water matrix (0.001–0.009pgμL−1 and 0.003–0.022pgμL−1, respectively), recoveries ranging 97–108%, inter- and intra-day precisions below 6.0% and 8.2%, respectively, for all PAHs. A comparison with other methods reported in literature demonstrates the reliability of such easy, cost-effective and reproducible methods. Finally, applications to nine different water samples are reported and discussed.

Rapid characterization of trace aflatoxin B1 in groundnuts, wheat and maize by dispersive liquid-liquid microextraction followed by direct electrospray probe tandem mass spectrometry.

Aflatoxins are poisonous and cancer-related chemical compounds commonly found in crops and plants. Aflatoxin B1 is the most toxic compound among aflatoxins and has been classified as group 1 carcinogenic to humans, especially in liver cancer. Herein, an ambient mass spectrometric method was developed for rapid characterization of trace aflatoxin B1 in peanuts. Direct electrospray probe tandem mass spectrometry (DEP-MS/MS) was used to detect aflatoxin B1 in peanuts. To avoid the matrix effect, the aflatoxin B1 in the samples was extracted and concentrated by dispersive liquid-liquid microextraction. The mass spectrometer was operated in the positive ion mode to monitor the intact molecular ion (m/z 313, MH+ ) and product ion (m/z 241) of aflatoxin B1 using multiple reaction monitoring. Since no clean-up procedure of the sample was required, the sampling step and the subsequent mass spectrometric detection of the aflatoxin B1 was completed in less than 5min. The limit of detection of aflatoxin B1 is at the sub-ppb level. The results obtained by DEP-MS/MS were also validated by liquid chromatography/tandem mass spectrometry (LC/MS/MS). Recovery of aflatoxin B1 in the sample was evaluated by analyzing spiked aflatoxin B1 with LC/MS/MS to be 85% and DEP-MS/MS to be 84%. DEP-MS/MS combined with a simple dispersive liquid-liquid microextraction procedure was successfully used for the quantitative analysis of AFB1 in nut samples. Due to its high efficiency, it is promising in providing important toxicological information for food safety in the real world. Copyright © 2017 John Wiley & Sons, Ltd.

Dispersive liquid-liquid microextraction for a rapid determination of glyoxal in alcoholic beverages

Carbonyl compounds, like glyoxal, methylglyoxal, diacetyl or pentane-2,3-dione, among others, have been widely studied. Besides its endogenous origin, they are originated from foodstuffs and are related to sensorial characteristics in products such as wine and beer. Generally, for their determination, the analytes must be derivatised to adapt them for the detection system and this step takes long time. The main aim of this research was to develop a simultaneous derivatization and extraction method which takes place in only few minutes. 3,4-diaminopyridine, as derivatizing reagent, generate a fluorescent product. This reaction is selective for glyoxal. For this new dispersive liquid-liquid microextraction (DLLME) procedure combined with chromatographic determination of glyoxal, various parameters affecting the extraction were optimized and finally, a mixture of butan-1-ol as dispersant solvent and dichloromethane as extractant solvent were selected. Its chromatographic peak appears at 2.6min. Four Spanish wines and five Spanish beers have been analysed and the results showed that the levels of glyoxal are comprised between 2.8–9.5mgL−1. The proposed DLLME method drastically reduces the reaction time from 2 or 3–20min improving the methods found in the literature. The glyoxal concentration found in the wines and beers analysed do not suppose any health risk.

A sensing colorimetric method based on in situ formation of gold nanoparticles after dispersive liquid-liquid microextraction for determination of zineb

A novel and highly efficient dispersive liquid–liquid microextraction (DLLME) based on the use of gold nanoparticles (AuNPs) plasmon resonance was developed for the determination of trace amounts of zineb pesticide. The label-free AuNPs as colorimetric probes were synthesized in situ into organic phase using a simple and rapid DLLME procedure. The presence of zineb affected on the plasmon absorbance of AuNPs in sedimented phase which allows the microvolume spectrophotometric sensing of this pesticide. Under the optimal conditions, the method is capable of determining zineb over a range of 0.8–20.0ngmL−1 with a limit of detection 0.55ngmL−1. The formation of the stable and dispersed AuNPs in organic phase provides a good precision for suggested DLLME method resulting in the relative standard deviation of 4.6 and 1.0% for 8 and 16ngmL−1 of zineb, respectively. The method was also successfully applied to the determination of zineb in the environmental samples with the recoveries in the range of 95.6–101.0% for the spiked samples.

Deep eutectic solvents for the purification of chloromycetin and thiamphenicol from milk.

Deep eutectic solvents were used in both dispersive liquid-liquid microextraction and solid-phase extraction for the purification of chloromycetin and thiamphenicol from milk. In the dispersive liquid-liquid microextraction procedure, deep eutectic solvents mixed with chloroform at different ratios (0:1-5:1, v/v) were used as the extraction agent to optimize the procedure, and the ratio of 2:1 v/v was found to be the best extraction agent with 87.23 and 83.17% recoveries of chloromycetin and thiamphenicol, respectively. Furthermore, deep eutectic solvents were also used to modify molecular imprinted polymers in solid-phase extraction procedure, and the polymers were used to purify chloromycetin and thiamphenicol from milk. Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy were used to characterize the polymers. The solid-phase extraction recoveries with deep eutectic solvents with molecularly imprinted polymers (chloromycetin and thiamphenicol, two templates), molecularly imprinted polymers (without deep eutectic solvents), and nonimprinted polymers (without a template) for chloromycetin were 91.23, 82.64, and 57.3%, respectively, and recoveries for thiamphenicol were 87.02, 79.03, and 52.27%, respectively. The recoveries of chloromycetin and thiamphenicol from milk in the solid-phase extraction procedure were higher than using deep eutectic solvents mixed with chloroform as the extraction agent in the dispersive liquid-liquid microextraction procedure.

PAH Residues in Honey by Ultrasound-Vortex-Assisted Liquid-Liquid Micro-Extraction Followed by GC-FID/IT-MS

Polycyclic aromatic hydrocarbon (PAH) residue concentrations have been measured in honey samples collected on the Italian market. An ultrasound-vortex-assisted dispersive liquid-liquid micro-extraction (UVALLME) procedure coupled with a gas chromatography flame ionization detector or ion trap mass spectrometry (GC-IT/MS) is proposed for fast analysis of fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(b)fluoranthene, benzo(a)pyrene, and benzoperylene. Different analytical parameters such as extraction solvent and relative volume, best extraction time, pH, NaCl concentration, and reproducibility at low and high concentrations were optimized. Under optimal conditions, the recoveries range from 95 to 107% and correlation coefficients range from 0.893 to 0.995 whereas the limits of detection (LODs) and limits of quantification (LOQs) are ≥36 and ≥41 ng g−1 in GC-FID and 0.030 and 0.069 ng g−1 in GC-IT/MS, respectively. The precision, expressed as relative standard deviations (RSDs), is ≤7.4 and ≤5.2% for low and high PAH concentration levels, respectively. The whole proposed methodology, demonstrated to be simple, reproducible, and sensible, has been applied to the determination of trace PAHs in five honey samples.

Recent Advances in Analysis of Pesticides in Food and Drink Samples Using LPME Techniques Coupled to GC-MS and LC-MS: a Review.

Food quality and food safety are major challenges affecting agricultural and industrial aspects of production. Many contaminants from different sources contaminate foods and drinks, leading to disastrous health problems like gene mutations and cancer. Previously, many different methods have been used for the analysis of these contaminants. Liquid-liquid extraction (LLE) has been the most well-known conventional technique used, but its limitations are its tediousness, time required, and the use of large quantities of toxic organic solvents. These limitations have led to the search for other, efficient techniques that are more environmentally friendly. Hence, this review highlights recent advances in liquid-phase (single-drop, hollow fiber, and dispersive liquid-liquid) microextraction procedures for food and drink analyses. Such modifications can be justified for solving limitations associated with the traditional LLE method. The objective of this review is to serve as a reference platform for providing effective management tools for solving problems of pollution, clean-up, and control of food quality and safety globally.

Simplified Determination of Organophosphorus Pesticides in Camellia Oil

ABSTRACTA rapid, simple, and economical analytical approach has been developed and evaluated for the determination of six organophosphorus pesticides in camellia oil. This method is based on dispersive liquid−liquid microextraction (DLLME) following simple extraction. Oil was extracted with methanol by a high-speed blender and filtered with glass paper to remove fat. The filtrate was incorporated in the DLLME procedure. Acetonitrile was used as the dispersive solvent and chloroform as the extraction solvent. The residues were analyzed by gas chromatography–mass spectrometry. Under the optimized conditions, the recoveries were between 78.4 and 112.8% with relative standard deviations less than 12.3%. The limits of detection for the analytes were from 0.0003 to 0.0056 mg · kg−1. The optimized method was used for the determination of organophosphorus pesticides in camellia oil.

Rapid determination of some beta-blockers in complicated matrices by tandem dispersive liquid-liquid microextraction followed by high performance liquid chromatography.

In this research work, an efficient tandem dispersive liquid-liquid microextraction (TDLLME) procedure coupled with high performance liquid chromatography-ultraviolet detection (HPLC-UV) was successfully applied for thedetermination of beta-blockers in human plasma and pharmaceutical wastewater samples. High clean-up and preconcentration factor are easily and rapidly feasible via this novel, cheap, and safe microextraction method, leading to high quality experimental data. It consists of two sequential dispersive liquid-liquid microextraction methods, accomplished via air/ultrasonic agitation and air agitation, respectively. In order to enrich the optimal values for the mentioned procedures, the Box-Behnken design (BBD) combined with the desirability function (DF) was used. The optimum values were found to be 11.0% (w/v) of the salt amount, an initial pH value of 12.0, 103μL of organic extractant phase, and 45μL of aqueous extractant phase with pH value of 2.0, resulted in reasonable recovery percentages with a logical desirability. Under optimal experimental conditions, good linear ranges (3-2000ngmL-1 for metoprolol and 2.5-2500ngmL-1 for propranolol with the correlation of determinations (R 2s) higher than 0.99) and low limits of detection (0.8 and 1.0ngmL-1 for propranolol and metoprolol, respectively) were obtainable. Also, TDLLME-HPLC-UV provided good proper repeatabilities (relative standard deviations (RSDs) below 5.7%, n = 3) and high enrichment factors (EFs) of 75-100. Graphical abstract TDLLME of beta-blockers from complicated matrices.

Dispersive liquid–liquid microextraction of quinolones in porcine blood: Optimization of extraction procedure and CE separation using experimental design

A dispersive liquid-liquid microextraction procedure was developed to extract nine fluoroquinolones in porcine blood, six of which were quantified using a univariate calibration method. Extraction parameters including type and volume of extraction and dispersive solvent and pH, were optimized using a full factorial and a central composite designs. The optimum extraction parameters were a mixture of 250 μL dichloromethane (extract solvent) and 1250 μL ACN (dispersive solvent) in 500 μL of porcine blood reached to pH6.80. After shaking and centrifugation, the upper phase was transferred in a glass tube and evaporated under N2 steam. The residue was resuspended into 50 μL of water-ACN (70:30, v/v) and determined by CE method with DAD, under optimum separation conditions. Consequently, a tenfold enrichment factor can potentially be reached with the pretreatment, taking into account the relationship between initial sample volume and final extract volume. Optimum separation conditions were as follows: BGE solution containing equal amounts of sodium borate (Na2 B4 O7 ) and di-sodium hydrogen phosphate (Na2 HPO4 ) with a final concentration of 23 mmol/L containing 0.2% of poly (diallyldimethylammonium chloride) and adjusted to pH 7.80. Separation was performed applying a negative potential of 25 kV, the cartridge was maintained at 25.0°C and the electropherograms were recorded at 275 nm during 4 min. The hydrodynamic injection was performed in the cathode by applying a pressure of 50 mbar for 10 s.