Acid-based deep eutectic solvents followed by GFAAS for the speciation of As(III), As(V), total inorganic arsenic and total arsenic in rice samples.

In the present study, an efficacious, safe, inexpensive and eco-friendly microextraction was provided by deep eutectic solvents based on dispersive liquid-liquid microextraction (DLLME - DES) followed by GFAAS. A series of DESs were synthesised using l-menthol as hydrogen bond acceptor (HBA) and carboxylic acids with 4, 6, 8 and 10 carbon atoms as hydrogen bond donors (HBD). The synthesised DESs were used as extractants of arsenic ions. Under optimised conditions, good linearity with coefficient of determination (r2) 0.992 and an acceptable linear range of 0.3-100 µg kg-1 was obtained. The limit of detection was 0.1 µg kg-1 (S/N = 3) for arsenite (As(III)) ions, and a high enrichment factor (EF = 200) was obtained. The enhancement factor and extraction recovery (ER%) of the method were 340 and 60%, respectively. RSDs including inter- and intra-day ranged from 3.2% to 5.8% in three examined concentrations. After a specific digestion, the capability of the synthesised DES in the extraction of As(III) from rice was tested. Total inorganic arsenic was separated similarly after reduction of arsenate (As(V)) to As(III), and As(V) concentration was calculated by difference. Using a second digestion method, total arsenic concentration (sum of organic and inorganic arsenic) in the samples was determined.

Application of magnetic dispersive solid phase extraction combined with solidification of floating organic droplet-based dispersive liquid-liquid microextraction and GC-MS in the extraction and determination of polycyclic aromatic hydrocarbons in honey.

A magnetic dispersive solid phase extraction method combined with solidification of floating organic droplet-based dispersive liquid-liquid microextraction has been validated for the extraction of polycyclic aromatic hydrocarbons from honey samples. For this purpose, a carbonised cellulose-ferromagnetic nanocomposite was used as a sorbent through the magnetic dispersive solid phase extraction. For preparation of the sorbent, first, carbonised cellulose nanoparticles were created by treating cellulose filter paper with concentrated solution of sulfuric acid. Then, the prepared nanoparticles were loaded onto Fe3O4 nanoparticles through coprecipitation. In the extraction process, first, a few mg of the sorbent was added to the diluted honey solution and dispersed in it using vortex agitation. The particles were then separated and the adsorbed analytes were eluted with an organic solvent. The eluent was taken and after mixing with a water-immiscible extraction solvent was used in the following solidification of floating organic droplet-based dispersive liquid-liquid microextraction procedure. By performing the extraction process under the obtained optimum conditions, low limits of detection (0.08-0.17 ng g-1) and quantification (0.27-0.57 ng g-1), satisfactory precision (relative standard deviations ≤ 5.0%), and wide linear range (0.57-500 ng g-1) with great coefficients of determination (r2≥ 0.9986) were obtained.

Sensitive determination of daunorubicin in plasma of children with leukemia using pH-switchable deep eutectic solvents and HPLC-UV analysis.

An environmental friendly, fast, easy and inexpensive liquid-liquid microextraction (LLME) in combination with pH-switchable deep eutectic solvent (DES) method followed by HPLC was investigated for the separation and determination of daunorubicin (DNR) in human plasma samples. For this purpose, first, 9 DESs were prepared based on previous studies and their switchability in aqueous solution was evaluated by changing the pH. Non-switchable DESs were discarded and switchable DESs were used to extract DNR. The parameters affecting the extraction efficiency were optimized (DES type, volume of DES, concentration of KOH, volume of HCl, salt addition and extraction time). After optimizing the conditions and drawing the calibration curve, figures of merit were calculated. Relative standard deviations (%RSDs) based on 7 replicate with 50 µg L-1 of DNR in plasma were 2.7 for intra-day and 4.8 % for inter-day. A wide linear range from 0.15 to 200 µg L-1 was obtained. The detection limit of the method based on signal-to-noise 3 and the quantification limit of the method based on signal-to-noise 10 were 0.05 and 0.15, respectively. After spiking plasma samples with different concentrations of DNR, relative recoveries were obtained in the range of 91.0-107.8 %.

Acrylamide in potato chips in Iran, health risk assessment and mitigation.

This study aimed to determine the acrylamide content in potato chips sold in Kermanshah, Iran and assess the potential health concerns associated with acrylamide exposure. HPLC-DAD was used to analyse 120 samples across 40 brands. The possible non-carcinogenic risk index for adults was below 1 for all 40 brands (100%), but for children it was only below 1 for 9 brands (22.5%) and above 1 for 31 brands (77.5%). Regarding the possible carcinogenic risk index, for adults only 1 out of 40 brands rated > 10-4, whereas for children all brands rated > 10-4. This shows that children's exposure to acrylamide through potato chips consumption in Kermanshah can be considered a risk on cancer and exposure of adults requires attention and monitoring. The best way to reduce acrylamide in potato chips and associated health risks is to improve the production process, especially temperature and time.

Determination of vanillin in different food samples by using SMM/Au@ZIF-67 electrochemical sensor.

Vanillin is a popular flavoring agent in many food products. Simple, fast, and reliable quantification of this compound is crucial for the food industry. In this work, we have developed a new electrochemical sensor for accurate detection of vanillin in various real samples. The composite electrode was made of sodium montmorillonite nanoclay (SMM) and gold nanoparticles modified ZIF-67 (Au@ZIF-67), in which SMM contributes to the large adsorption capacity of the analyte, ZIF-67 and SMM supply more sensing active sites, and gold nanoparticles provide high electrical conductivity. The sensing electrode was comprehensively characterized using Brunauer-Emmett-Teller, EDS, XRD, SEM, FTIR, and TEM, and its electrochemical behavior for determination of vanillin including the electrooxidation mechanism of vanillin and different parameters such as scan rate and pH value was investigated. The result revealed that a two electron-two proton process was involved in the electrooxidation of vanillin, which takes place more readily due to the lower potential on the surface of SMM/Au@ZIF-67/carbon paste electrode. The new composite electrode was also more sensitive to vanillin detection with an anodic peak current almost 2.6 times more than that of the bare electrode. A linear sensing concentration range was established between 1 and 1200 nM with a detection limit of 0. 3 nM and a limit of quantitation of 1 nM. For real samples, the sensor demonstrated excellent recovery rates and reliability that was comparable to the standard high-performance liquid chromatography method.

A national systematic literature review for aflatoxin M1 in commonly consumed cheese brands in Iran: Human health risk assessment by Monte Carlo simulation.

Cheese is popular in Iran because of its high nutritional value; therefore, it is necessary to control this product regarding health risk factors, particularly aflatoxin M1 (AFM1). This research reviewed AFM1 in various varieties of cheese in Iran to assess the potential health risks associated with consuming these products for different age groups. In this regard, all accessible papers from different databases were screened between June 27, 2000 and October 10, 2022 b y systematic research and then considering the selection criteria of the studies; finally, 22 articles were selected for the current review. The amount and prevalence of AFM1 were calculated and separated based on the cheese variety, and the sampling location; health risk assessment (HRA), statistical, uncertainty, and sensitivity analysis for AFM1 of cheese for different age groups were performed. The study results for 2143 samples showed that the overall average AFM1 for cheese is 160 ± 175 ng/kg, below the European Commission (EC) regulation (250 ng/kg). AFM1 contaminated 72.42% of all cheese samples, and 13% of these contaminated samples had a higher AFM1 than the EC regulation. Cheese varieties were ranked based on average levels of AFM1 as white pasteurized > traditional > creamy > probiotic > Lighvan, and this ranking was obtained based on sampling locations as market > dairy factories > livestock farms. Based on the HRAs, from the perspective of the liver cancer risk (LCR), the margin of exposure (MOE), and the hazard index (HI) approach, it can be concluded that cheese produced in Iran, in terms of AFM1, particularly for children, poses serious health risks. Accordingly, it is imperative to carefully consider implementing suitable management methods to inhibit the growth of aflatoxin B1 (AFB1) in livestock fodder, and training in sanitary production and processing of dairy products according to world standards is suggested for industrial and traditional cheese producers across Iran.

Chalcopyrite as an oxidants activator for organic pollutant remediation: A review of mechanisms, parameters, and future perspectives.

Advanced oxidation processes (AOPs) based on oxidants have attracted attention for the degradation of organic pollutants. The combination of chalcopyrite with oxidants such as persulfate, peroxide, percarbonate, and others shows promise as a system due to its ability to activate through various pathways, leading to the formation of numerous radical and non-radical species. In this review, the generation of sulfate radical (SR) and hydroxyl radical (HR) in AOPs were summarized. The significance of chalcopyrite in various approaches including Fenton, photo-Fenton, and photo/Fenton-like methods, as well as its involvement in electrochemical Fenton-based processes was discussed. The stability and reusability, toxicity, catalyst mechanism, and effects of operational parameters (pH, catalyst dosage, and oxidant concentration) are evaluated in detail. The review also discusses the role of Fe2+/3+, Cu1+/2+, S2- and Sn2- present in CuFeS2 in the generation of free radicals. Finally, guidelines for future research are presented in terms of future perspectives.

Evaluation of blood lead levels in opium addicts and healthy control group using novel deep eutectic solvent based dispersive liquid-liquid microextraction followed by GFAAS.

Today, drug dealers and sellers add lead compounds to these substances to get more profit. As a result, drug users are heavily exposed to lead, and lead poisoning is clearly seen in most of them. Therefore, it is especially important to check the blood lead levels in these people. In this research, an efficient and eco-friendly pretreatment method was established by deep eutectic solvent for dispersive liquid-liquid microextraction (DES - DLLME) followed by graphite furnace atomic absorption spectrometry (GFAAS) analysis. The selected hydrophilic deep eutectic solvent consists of l-menthol and (1S)-( +)-camphor-10-sulfonic acid (CSA) at a 5:1 molar ratio as a green solvent instead of traditional toxic organic solvents. Under the optimal extraction conditions, the introduced method exhibited good linearity with coefficient of determination (r2) 0.9975 and an acceptable linear range of 0.3-80 µg L-1. Accordingly, the detection limit was 0.1 µg L-1 (S/N = 3) for lead ions, and the high enrichment factor (240) was obtained. The proposed method was successfully applied to analysis lead ions in real blood samples, which is a promising technique for biological samples. The case samples were classified and analyzed based on age, duration of consumption, and type of substance. The results showed that there was no significant difference between blood lead levels in different age groups and different duration of use, while blood lead levels were higher in opium residue (shireh) users than in opium users.

Trace determination of triazine herbicides in fruit and vegetables using novel hydrophobic deep eutectic solvent-based dispersive liquid-liquid microextraction followed by high-performance liquid chromatography-ultraviolet.

In the present research, a novel hydrophobic deep eutectic solvent-based dispersive liquid-liquid microextraction technique was established and combined with high-performance liquid chromatography-ultraviolet for the determination of triazine herbicides in fruit and vegetable samples. A deep eutectic solvent was synthesized using l-menthol as a hydrogen bond acceptor and ethylene glycol as a hydrogen bond donor and used as a green extractant. The characterization of deep eutectic solvent was investigated by Fourier-transform infrared, nuclear magnetic resonance, and thermogravimetric analysis. Under the optimum conditions, relative standard deviation values for intra-day and inter-day of the method based on seven replicate measurements of 50.0 µg/kg of triazines were in the range of 2.8%-5.5% and 3.7%-7.2%, respectively. The calibration graphs were linear in the range of 3.0-500 µg/kg and the limits of detection were in the range of 1.0-2.0 µg/kg. The relative recoveries of different fruit and vegetable samples that have been spiked with two levels of target compounds were 91.5%-109.8%. The method has good linearity, sensitivity, accuracy, and precision. It is also environmentally friendly and was successfully used to determine the concentrations of triazines in fruit and vegetable samples.

Quantitative analysis and carcinogenic/non-carcinogenic risk assessment of aflatoxin M1 in milk-based baby food and infant formula milk - a case study in Iran.

In this study, solid-phase extraction (SPE) combined with the dispersive liquid-liquid microextraction based on novel hydrophobic deep eutectic solvent (DLLME - DES) has been developed as an ultra-pre-concentration technique for the extraction of aflatoxin M1 (AFM1) in milk-based baby food (MBBF) and infant formula milk (IFM) samples followed by HPLC combined with fluorescence detection (HPLC - FL). In addition, carcinogenic and non-carcinogenic risk assessment was performed by health-related risk factors including liver cancer risk (LCR), margin of exposure (MOE) and target hazard quotient (THQ) were calculated using the mean of AFM1 in different infant food samples. The results of the study showed that the mean of AFM1 was statistically significant different between various brands and types of IFM and MBBF. The results of the study showed that the percentage of positive samples higher than the allowable limit of AFM1 in 36 samples of domestic infant formula milk (DIFM), 24 samples of imported infant formula milk (IIFM), 36 samples of domestic milk-based baby food (DMBBF) and 18 samples of imported milk-based baby food (IMBBF) were 41.6, 12.5, 66.7 and 33.3%, respectively. In addition, estimated values for health risk-related factors including LCR, MOE and THQ indicated that for most infants less than one-year-old were higher than the acceptable levels. Based on the results, it can be concluded that the quality of IFM and MBBF consumed in Iran in terms of AFM1 is poor. Therefore, it is necessary to take appropriate measures to reduce the amount of AFM1 in DIFM and DMBBF, and in addition, the IIFM and IMBBF should be controlled qualitatively before supplying the market.

Novel deep eutectic solvent-based liquid phase microextraction for the extraction of estrogenic compounds from environmental samples.

Steroid hormones, such as estrone (E1), 17ß-estradiol (E2), 17ß-ethinylestradiol (EE2) and estriol (E3) are a group of lipophilic active substances, synthesized biologically from cholesterol or chemically. A pH-switchable hydrophobic deep eutectic solvent-based liquid phase microextraction (DES-LPME) technique was established and combined with gas chromatography-mass spectroscopy for the determination of estrogenic compounds in environmental water and wastewater samples. A DES was synthesized using l-menthol as HBA and (1S)-(+)-camphor-10-sulfonic acid (CSA) as HBD, and used as a green extraction solvent. By adjusting the pH of the solution, the unique behavior of the DES in the phase transition and extraction of the desired analytes was investigated. The homogenization process of the mixture is done only by manual shaking in less than 30 seconds and the phase separation is done only by changing the pH and without centrifugation. Some effective parameters on the extraction and derivatization, such as molar ratio of DES components, DES volume, KOH concentration, HCl volume, salt addition, extraction and derivatization time and derivatization prior or after extraction were studied and optimized. Under the optimum conditions, relative standard deviation (RSD) values for intra-day and inter-day of the method based on 7 replicate measurements of 20 ng L-1 of estrogenic compounds and 10 ng L-1 for internal standard in different samples were in the range of 2.2-4.6% and 3.9-5.7%, respectively. The calibration graphs were linear in the range of 0.5-100 ng L-1 and the limits of detection (LODs) were in the range of 0.2-1.0 ng L-1. The relative recoveries of environmental water and wastewater samples which have been spiked with different levels of target compounds were 91.0-108.8%.

Sensitive determination of vincristine in plasma of children with leukaemia using vortex-assisted dispersive liquid-liquid microextraction based on hydrophobic deep eutectic solvent.

Vincristine has a wide spectrum of clinical activity and is currently used in the treatment of leukemia. Despite its high therapeutic properties, vincristine has common side effects. Accordingly, it is desirable to determine vincristine in plasma for the use of the drug with strict monitoring. In the present research, for the first time a hydrophobic deep eutectic solvent (DES) composed of methyltrioctylammonium chloride (MTOAC) and n-butanol in a molar ratio of 1 : 3 was used as the extractant in dispersive liquid-liquid microextraction (DLLME) for the extraction and determination of vincristine in the plasma of children with leukemia prior to its analysis by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). Under optimal experimental conditions, the method showed good linearity with a correlation coefficient (R 2) of 0.9986 in the linear range of 0.06-300 µg L-1, low limit of detection of 0.02 µg L-1 and acceptable extraction efficiency (EE) of 88.4%. In the final stage of the study, this proposed technique was successfully applied to determine vincristine in real plasma, and the obtained results demonstrated the ability of the synthesized DES to extract drugs from biological fluids.

Extraction and determination of strobilurin fungicides residues in apple samples using ultrasound-assisted dispersive liquid-liquid microextraction based on a novel hydrophobic deep eutectic solvent followed by H.P.L.C-U.V.

In this study, several novel and natural hydrophobic deep eutectic solvents (D.E.Ss) were prepared using methyl trioctylammonium chloride (M.T.O.A.C) as H.B.A and different types of straight chain alcohols as H.B.Ds. One of the D.E.Ss composed of M.T.O.A.C and n-butanol was advantageously used to develop an ultrasound-assisted dispersive liquid-liquid microextraction (U.A-D.L.L.M.E) method combined with high-performance liquid chromatography-ultraviolet detection (H.P.L.C-U.V) for the determination of some strobilurin fungicides in apple samples. Several important parameters influencing extraction efficiency were investigated and optimised, including the type and volume of extractant in ultrasound stage, sonication time, the type and volume of D.E.S, sample solution pH and effect of salt addition. Under optimal experimental conditions, the method showed good linearity with correlation coefficients (R2) of 0.9985 - 0.9991 in the linear range of 4-1500 µg kg-1, low limits of detection of 1.5-2 µg kg-1 and acceptable extraction recoveries in the range of 76-92%. Enrichment factor was in the range of 95-115. The proposed method was successfully applied for the extraction and preconcentration of trace fungicides in apple samples, and the results demonstrated the potential of the synthesised D.E.S for the extraction and determination of contaminants in aqueous samples.

Countercurrent Salting-out Homogenous Liquid-Liquid Extraction and Dispersive Liquid-Liquid Microextraction Based on the Solidification of Floating Organic Drop Followed by High-Performance Liquid Chromatography for the Isolation and Preconcentration of Pesticides from Fruit Samples.

BACKGROUND: Pesticides are widely used to control pests and prevent diseases in crops, including cereals, vegetables, and fruits. Due to factors such as the persistence of pesticides, bioaccumulation, and potential toxicity, pesticide residue monitoring in foodstuffs is very important. OBJECTIVE: In the current research, we proposed a novel approach using countercurrent salting-out homogenous liquid-liquid extraction combined with dispersive liquid-liquid microextraction based on the solidification of floating organic droplets (DLLME-SFO) for isolation and preconcentration of pesticides from aqueous samples for analysis by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). METHODS: In brief, sodium chloride was used as a separation reagent, in a small glass column, through which was passed a mixture of an aqueous solution of, for example, fruit juice and acetonitrile. In this process, the droplets rose through the column and a separated layer would be formed on the remained an aqueous phase. Following that, acetonitrile as the organic phase was mixed with 50.0 µL of 1-undecanol (extraction solvent). To further enrich the analytes, the mixture was injected into 5 mL of a 4% w/v sodium chloride solution and placed in a tube for the DLLME-SFO. RESULTS: Under optimal conditions, a dynamic linear range of 0.5-500 µg/L, extraction recovery of 65-85%, enrichment factors of 108-142, and limit of detection of 0.2-0.4 µg/L were obtained for the organophosphorus pesticides analysed. In addition, the repeatability and reproducibility from five replicate measurements of the pesticides (100 µg/L) were within the ranges of 3.5-5.1% and 4.5-6.3%, respectively . CONCLUSION: In this research, a new extraction method based on countercurrent salting out homogeneous liquid-liquid extraction combined with DLLME-SFO has been applied for the determination of pesticide residues in fruits, juice and environmental samples before using HPLC-UV analysis. The combined method not only leads to high enrichment factors, but can also be used in complex matrices (such as fruits, juices and high-salt solutions) without pre-treatment or dilution. Compared with other sample preparation methods, this analysis procedure has many advantages, including simplicity, ease of operation, high pre-enrichment factor, low detection limit and relatively short analysis time. HIGHLIGHTS: Combination of CCSHLLE and DLLME-SFO was applied for the analysis of organophosphorous pesticide residues in fruit, fruit juices and environmental samples. The DLLME-SFO method avoided using high density and toxic extraction solvents. LODs are achievable at ng L-1 using CCSLLE-DLLME-SFO-HPLC-UV.

Polycyclic aromatic hydrocarbons in grilled foods from Kermanshah province.

Grilling is one of the most traditional ways of cooking foods, especially meat, which can produce a number of carcinogenic compounds. This study was to identify the pattern of kebab consumption and its PAHs among a selection of the Iranian population. Kebab consumption pattern were assessed using a validated questionnaire. A sample of three types of popular kebabs, including Koobideh (minced meat), Barg (crushed meat pieces), and Juje (chopped chicken pieces), was collected from each restaurant and then transferred to a laboratory to measure PAHs. The median benzo[a]pyrene concentrations (7.85 µg/kg) and the sum of benzo[a]pyrene, chrysene, benzo[a]anthracene, and benzo[b]fluoranthene concentrations (15.74 µg/kg) were higher than the maximum level imposed by the Commission of the European Communities. A significant relationship between Barg kebab prepared with charcoal and the amounts of anthracene, benzo[a]anthracene, dibenzo[a,h]pyrene, and benzo[g,h,i]perylene was found. The highest PAHs produced in samples prepared with charcoal was dibenzo[a,h]pyrene.

Sensitive determination of methotrexate in plasma of children with acute leukemia using double-solvent supramolecular systemas a novel extractant for dispersive liquid-liquid microextraction.

Methotrexate, as a folate antagonist, is one of the first anti-neoplasm drugs offered and is still used as an effective drug in the treatment of various malignancies. Methotrexate has a narrow treatment index and is associated with numerous side effects.In thisresearch, for the first time a double-solvent supramolecular system (DSS) was developed as an extractant without disperser solvent for dispersive liquid-liquid microextraction (DLLME). DSS - DLLME was applied to the extraction of methotrexate in plasma of children with acute leukemiaprior to itsdetermination by high-performance liquid chromatography-ultraviolet detection (HPLC - UV). In the present method, two long normal chain alcohols are mixed in a particular ratio, and then it is injected into the sample solution, which is on the magnetic stirrer. In this case, the mixture of the two alcohol changes to new supramolecular aggregate. This new supermolecule is used as an extractant, which has a higher extraction power than any of its components alone. Under the optimum conditions, the calibration graph was linear in the rage of 0.1-150 µg L-1 with detection limit of 0.03 µg L-1. Relative standard deviations (RSDs) including intra-day and inter-day of method based on7 replicate determinations of 100.0 µg L-1of methotrexate were 2.6% and 4.8%,respectively. The results proved that DSS - DLLME is a sensitive, very simple, inexpensive, environmental friendly, rapid and efficient method for the preconcentration of trace amount of drugs in biological samples.

Novel hydrophobic deep eutectic solvent for vortex-assisted liquid phase microextraction of common acaricides in fruit juice followed by HPLC-UV determination.

In the present research, several novel and natural hydrophobic deep eutectic solvents (DESs) were prepared using methyltrioctylammonium chloride (MTOAC) as the hydrogen bond acceptor (HBA) and different types of straight chain alcohols as hydrogen bond donors (HBDs). One of the DESs composed of MTOAC and n-butanol was advantageously used to develop a vortex-assisted liquid phase microextraction (VALPME) method combined with high-performance liquid chromatography-ultraviolet detection (HPLC-UV) for the determination of common acaricides in fruit juice samples. Several important parameters influencing extraction efficiency were investigated and optimized, including the type and volume of DES, sample solution pH, effect of salt addition and, extraction and vortex time. Under optimal experimental conditions, the method showed good linearity with the correlation coefficients (R 2) of 0.9986-0.9991 in the linear range of 2-300 µg L-1, low limits of detection of 0.5-1 µg L-1 and acceptable extraction recoveries in the range of 85-93%. The proposed method was successfully applied for the extraction and preconcentration of trace acaricides in real fruit juice samples, and the results demonstrated the potential of the synthesized DESs for the extraction and determination of contaminants in aqueous samples.

Sensitive determination of deferasirox in blood of patients with thalassemia using dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by HPLC-UV.

Deferasirox is an oral iron chelator that has been on the market since 2005 and has been a suitable replacement for injectable chelators. It is important to check the amount of this drug in the blood of patients due to side effects. In this study, a new dispersive liquid-liquid microextraction based on solidification of floating drganic drop (DLLME - SFO) was applied to the extraction of deferasirox in the blood of patients with thalassemia prior to its analysis by high-performance liquid chromatography-ultraviolet detection (HPLC - UV). In this method, two long alcohols of the normal chain are mixed in a particular ratio, and then it is injected into the sample solution, which is on the magnetic stirrer. In this case, the mixture of the two alcohol changes to new double-solvent aggregate. This new double-solvent system is used as an extractant, which has a higher extraction power than any of its components alone. Under the optimum conditions, the calibration graph was linear in the rage of 0.2-200 µg L-1 with detection limit of 0.06 µg L-1. Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 100.0 µg L-1of deferasirox were 3.8 % and 5.7 %, respectively. The results showed that DLLME - SFO is a very simple, inexpensive, environmental friendly, sensitive and efficient analytical method for the determination of trace amount of drugs in biological samples and suitable results were obtained.

The speciation of inorganic arsenic in soil and vegetables irrigated with treated municipal wastewater.

In this research, an environmental friendly, green and efficient sample preparation method using vortex-assisted microextraction based on a deep eutectic solvent (VAME-DES) followed by graphite furnace atomic absorption spectrometry (GFAAS) was developed for the preconcentration and determination of As(iii)/As(v) and total inorganic arsenic in soil and vegetables irrigated with treated municipal wastewater from Tehran and Kermanshah, Iran. In the proposed method, a novel DES, characterized by its low density, was prepared by mixing choline chloride and citric acid monohydrate at a molar ratio of 1 : 1. Under optimal conditions, the proposed method enabled the achievement of a good enrichment factor of 175. The calibration graph was linear in the range of 0.3-100 µg kg-1 and the limit of detection (LOD) was 0.10 µg kg-1. The repeatability and reproducibility of the method based on seven replicate measurements of 50 µg kg-1 As(iii) in analysed samples were 4.2% and 6.5, respectively. The relative recoveries from soil and vegetables that were spiked with different levels of As(iii) and As(v) were 94.2-104.3 and 91.0-107.0%, respectively. The main advantage of the proposed method is the use of a non-toxic and non-volatile DES instead of volatile organic solvents. The accuracy of the proposed procedure was also assessed by the speciation of arsenic in two standard reference materials (GBW10014 cabbage and GBW10015 spinach). The extraction methodology is simple, rapid, cheap and green, since only small amounts of non-toxic solvents are necessary.

Determination of common organophosphorus pesticides in the blood of children with acute leukaemia using a double-solvent system as a novel extractant for dispersive liquid-liquid microextraction.

In this research, a new mode of dispersive liquid-liquid microextraction based on a double-solvent system (DLLME-DSS) was developed for the extraction and preconcentration of organophosphorus pesticides (OPPs) in the blood of children with acute leukaemia prior to determination by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). In the present method, two long normal chain alcohols are mixed in a particular ratio, and then injected into the sample solution, which is magnetically stirred. In this case, the mixture of the two alcohols changes to a new aggregate extractant. This new double-solvent is used as an extractant, which has a higher extraction power than any of its components alone. Under the optimum conditions, the calibration graph was linear in the rage of 3-600 µg L-1 with detection limits of 1 to 2 µg L-1. Relative standard deviations (RSDs) including intra-day and inter-day of the method based on 7 replicate determinations of 100.0 µg L-1 for each analyte were in the range of 2.9-4.7% and 3.8-6.1%, respectively. The results proved that DLLME-DSS is a sensitive, very simple, inexpensive, environmentally friendly, rapid and efficient method for the preconcentration of trace amounts of OPPs in blood samples.