Liquid-liquid Micro Research Articles

Synthesis and identification of meta-(4-bromobenzyloxy) benzaldehyde thiosemicarbazone (MBBOTSC) as novel ligand for cadmium extraction by ultrasound assisted-dispersive-ionic liquid-liquid micro extraction method

In this research, meta-(4-bromobenzyloxy) benzaldehyde thiosemicarbazone (MBBOTSC) as a novel ligand was synthesized from the reaction between meta-(4-bromobenzyloxy) benzaldehyde and thiosemicarbazide under basic condition in water and ethanol as solvents. Ligand has the ability to chelate ions and therefore, it was used to form a complex and extract ions. Then, the cadmium ions in water and wastewater samples were separated based on MBBOTSC by ultrasound assisted-dispersive-ionic liquid-liquid microextraction method (USA-D-ILLME) before determination by AT-F-AAS. The MBBOTSC ligand was added to the mixture of the ionic liquid/acetone (IL/AC, [OMIM][PF6]) and then injected by syringe to 50 mL of water samples at pH 6-7. The sample was put into the ultrasonic accessory for 5 minutes, after complexation (Ligand-Cd; RS…Cd….RS), the water sample was centrifuged for 3 min for phase separation. Due to complexation and back-extraction of Cd in liquid phase, the amount of Cd ions in the water samples was determined by AT-F-AAS . In optimized conditions, the Linear ranges and LOD for 50 mL of water samples were obtained 1-36 μg L-1 and 0.3 μg L-1, respectively (Mean RSD= 1.26%). The validation results were successfully achieved by spiking real samples and using ET-AAS.

Methamphetamine detection enabled by a fluorescent carborane derivative of perylene monoimide in film state

• A novel and highly emissive o -carborane derivative of perylene monoimide (PMI-CBH) was synthesized. • The PMI-CBH-based film is sensitive to gaseous methamphetamine with a detection limit lower than 1.4 ppb. • The film sensor also works to methamphetamine in human urines as low as 1.0 μg/mL. • A home-made conceptual sensor device was constructed. Rapid and on-site detection of illicit drugs in liquid phase remains a challenge for years. Herein, we report the synthesis of an o -carborane derivative of perylene monoimide ( P MI-CBH ) with high fluorescence quantum yield in solid state. The emission of the compound-based film is sensitive to the presence of methamphetamine (MAPA) in vapor phase with a detection limit (DL) lower than 1.4 ppb and a response time less than 2 s. With combination of liquid-liquid micro- extraction, the fluorescent film was successfully used for the detection of MAPA in aqueous phase including human urines even at a concentration lower than 1.0 μg/mL. Further tests revealed that commonly used anti-cold drugs showed little effect upon the sensing. Moreover, the film is photochemically stable and reusable, demonstrating its potential for real-life applications.

Menthol-Based Deep Eutectic Solvent Dispersive Liquid–Liquid Microextraction: A Simple and Quick Approach for the Analysis of Phthalic Acid Esters from Water and Beverage Samples

In this work, a natural deep eutectic solvent (NADES) composed of L-menthol:acetic acid 1:1 (molar ratio) was applied for the first time as extraction solvent for the dispersive liquid-liquid micro...

Ultrasonication Assisted Dispersive Liquid-liquid Micro Extraction (USA-DLLME) for Determination of Pyrene Concentration in Water

Pyrene is one of the chemical compounds of polycyclic aromatic hydrocarbons (PAHs) that has been reported as toxic, carcinogenic, and mutagenic which commonly found in water, food, soil, and air. Therefore, a study of ultrasonic assisted dispersive liquid-liquid microextraction (USA-DLLME) was conducted to extract pyrene from polluted water. The analytical parameters such as volume of extractant solvent, volume of disperser solvent, sonication time, and centrifugation speed were optimized using response surface method (RSM). Gas chromatography-flame ionization detector was used to analyse the pyrene content. The extraction recovery obtained for validation on real water based on optimization are in the range of 14.8%-49.8%. The low value of extraction recovery must be due to unsuitable types of extraction solvent used. However, this study have achieved all the objectives based on the developed method.

In-vitro extraction and separation of copper ions from human blood samples based on amoxicillin/clavulanic acid by ultrasound assisted-dispersive centrifuge liquid-liquid micro extraction

The low concentration of copper (Cu2+) can be effected on the central nervous system (CNS) and caused to multiple sclerosis (MS). Although many antibiotics can treat the bacterial infections but some of antibiotics decrease essential metal concentrations in human body and must be controlled by determining. In this study, in-vitro extraction of copper (Cu2+) with amoxicillin/clavulanic acid (AMOXC) has been studied due to interacting with metals. By procedure, Cu2+ ions were separated from blood samples by ultrasound assisted-dispersive centrifuge liquid-liquid micro extraction (USA-DC-LLME). The mixture of AMOXC (0.01 g), ionic liquid ([BMIM][PF6]) and acetone injected to 10 ml of serum blood sample at human pH=7.2. After extraction, the concentration of Cu2+ ions was determined by flame atomic absorption spectrometry (F-AAS). The LOD, enrichment factor (EF), linear range (LR) and working range (WR) were obtained 6 μg L-1, 9.92, 0.018-0.5 mg L-1 and 0.02-2.58 mg L-1, respectively (RSD<1.1%).

Application of dispersive liquid-liquid micro extraction combined with spectrophotometric technique for preconcentration and determination of cadmium using new organic reagent

A new organic reagent namely 5-(4- isopropoxy-6-(methyl amino)-5- nitrosopyrimidine-2-yl) diazenyl) quinolin-8-ol (IMNDQ) was synthesized, characterized and employed for the estimation of Cadmium (II) afterwards preconcentration using Dispersive liquid- liquid microextraction (DLLME). In this precocentration method, chloroform and methnol were used as extraction and disperser solvents respectively and the ligand 5-(4- isopropoxy-6-(methyl amino)-5- nitrosopyrimidine-2-yl) diazenyl) quinolin-8-ol was used as a reagent for the extraction of Cd (II), Visible spectrophotometry was used for the estimation of the analyte after preconcentration. The influence of various factors on the extraction was investigated, for example disperser and extraction solvent type, pH and concentration of chelating agent. At optimum condition, the enrichment factors of (95) was gotten, the calibration graph was linear in the range (20–100) ng. mL−1 Cd+2 with detection limit of (4.46) ng. mL−1 and relative standard deviation (RSD) for seven duplicate measurements of 60 ng. mL−1 of Cd+2 was (1.12)%.The method was used to the estimation of Cd+2 in some food samples.

Determination of malathion by homogeneous liquid-liquid micro extraction via flotation assistance combined with gas chromatography in water samples

A new preconcentration method termed, homogeneous liquid-liquid microextraction via flotation assistance (HLLME-FA) has been developed for the sensitive determination of Malathion in water samples. In this method, home-designed extraction cell was used for facile collection of organic solvent during the extraction procedure. The novel approach avoids the centrifugation step. In this extraction method, a mixture of toluene (extraction solvent) and acetone (homogeneous solvent) was added into a special vessel after addition of the sample solution. By using air flotation, the organic solvent was collected at the conical part of the designed cell. Parameters affecting the extraction efficiency such as type and volume of extraction and homogeneous solvents, ionic strength and extraction time were studied and optimized. The new method (HLLME-FA) provides detection limit of 0.1 µg L -1 and calibration graph was linear in the range of 1.0 - 200 µg L -1 . The results show that HLLME-FA is a suitable method for the determination of Malathion in water samples. KEY WORDS : Homogeneous liquid-liquid microextraction, Flotation assistance, Malathion, Gas chromatography, Water samples Bull. Chem. Soc. Ethiop. 2019 , 33(1), 1-10 DOI: https://dx.doi.org/10.4314/bcse.v33i1.1

Review on Recent Development and Application of Dispersive Liquid-Liquid Micro Extraction

Dispersive liquid-liquid micro extraction (DLLME) has become a very popular environmentally benign sample-preparation technique, due to its simplicity, rapidity of operation and low consumption of solvent and reagent. It has attracted much interest from scientist working in separation science and much improvement has been made since its introduction in 2006. It has been combined with different extraction techniques such as floating organic drop, solid-phase extraction, and supercritical fluid extraction. This seminar has focused on the review on development of dispersive liquid micro extraction (DLLME) and its application in different samples, such as water, soil, food and biological material with different analytical techniques. DOI : 10.7176/CMR/11-3-02 Publication date :March 31st 2019

Estimating the risk of phthalates exposure via tea consumption in general population

Four common phthalic acid esters (PAEs) levels in tea fusions samples prepared from three types of tea bags (green, black and white) of ten commercial brands were extracted from the infusions by a dispersive liquid-liquid micro extraction method and determined by GC-MS. PAEs were not found in white tea samples. Residue levels of total phthalic acid esters (TPAEs) in black and green teas showed no significant difference (median=367.5, Interquartile range=244.7-667.5 and median=381, Interquartile range=188.7-688.2µg/kg respectively). DEHP levels in green teas were significantly higher than those in black teas (Median= 93.5 and 204 respectively). Total phthalate esters (TPAEs) levels in flavored teas were about two-fold higher than in non-flavored teas. The four commercial brands tested contain significant levels of DEHP when compared to other brands. Essential oils and essences that were added to tea for improvement of color and taste could be the main sources of PAEs contamination. If oral absorption of phthalates were assumed to be 100%, the maximum daily exposure levels to TPAEs via tea consumption (due to consumption of 5 cups of tea prepared from the tea containing the highest levels TPAEs) were estimated to be 230e -4 μg/kg bw/Day, which are far lower than the regulation levels set by the expert panels on regularly toxicity.

Estimating the risk of phthalates exposure via tea consumption in general population

Four common phthalic acid esters (PAEs) levels in tea fusions samples prepared from three types of tea bags (green, black and white) of ten commercial brands were extracted from the infusions by a dispersive liquid-liquid micro extraction method and determined by GC-MS.PAEs were not found in white tea samples. Residue levels of total phthalic acid esters (TPAEs) in black and green teas showed no significant difference (median=367.5, Interquartile range=244.7-667.5 and median=381, Interquartile range=188.7-688.2µg/kg respectively). DEHP levels in green teas were significantly higher than those in black teas (Median= 93.5 and 204 respectively). Total phthalate esters (TPAEs) levels in flavored teas were about two-fold higher than in non-flavored teas. The four commercial brands tested contain significant levels of DEHP when compared to other brands. Essential oils and essences that were added to tea for improvement of color and taste could be the main sources of PAEs contamination. If oral absorption of phthalates were assumed to be 100%, the maximum daily exposure levels to TPAEs via tea consumption (due to consumption of 5 cups of tea prepared from the tea containing the highest levels TPAEs) were estimated to be 230e-4 μg/kg bw/Day, which are far lower than the regulation levels set by the expert panels on regularly toxicity.

Recent Trends in Microextraction Techniques Employed in Analytical and Bioanalytical Sample Preparation

Sample preparation has been recognized as a major step in the chemical analysis workflow. As such, substantial efforts have been made in recent years to simplify the overall sample preparation process. Major focusses of these efforts have included miniaturization of the extraction device; minimizing/eliminating toxic and hazardous organic solvent consumption; eliminating sample pre-treatment and post-treatment steps; reducing the sample volume requirement; reducing extraction equilibrium time, maximizing extraction efficiency etc. All these improved attributes are congruent with the Green Analytical Chemistry (GAC) principles. Classical sample preparation techniques such as solid phase extraction (SPE) and liquid-liquid extraction (LLE) are being rapidly replaced with emerging miniaturized and environmentally friendly techniques such as Solid Phase Micro Extraction (SPME), Stir bar Sorptive Extraction (SBSE), Micro Extraction by Packed Sorbent (MEPS), Fabric Phase Sorptive Extraction (FPSE), and Dispersive Liquid-Liquid Micro Extraction (DLLME). In addition to the development of many new generic extraction sorbents in recent years, a large number of molecularly imprinted polymers (MIPs) created using different template molecules have also enriched the large cache of microextraction sorbents. Application of nanoparticles as high-performance extraction sorbents has undoubtedly elevated the extraction efficiency and method sensitivity of modern chromatographic analyses to a new level. Combining magnetic nanoparticles with many microextraction sorbents has opened up new possibilities to extract target analytes from sample matrices containing high volumes of matrix interferents. The aim of the current review is to critically audit the progress of microextraction techniques in recent years, which has indisputably transformed the analytical chemistry practices, from biological and therapeutic drug monitoring to the environmental field; from foods to phyto-pharmaceutical applications.

Alterations in liver marker enzymes and recovery ability of cyprinids as indicators of aquatic pollution.

Information on the detection of pesticides in fresh water Lakes of Kashmir (Dal and Mansbal) through GC-MS technique is scarce, and also the recovery in biochemical parameters (AST, ALT and ALP) of fish after transferring them to clean media has not been reported yet. The water samples were collected from three sites and analyzed for their pesticide profile by dispersive liquid-liquid micro extraction (DLLME) followed by GC-MS. Influence of pesticides on liver marker enzymes of Cyprinus carpio and Carassius carassius was also investigated. The results obtained showed the presence of three main pesticides viz. chlorpyrifros, dimethoate and dichlorvos in waters of Dal Lake whereas no pesticide was detected in waters of Mansbal. The higher values for AST, ALT and ALP activities and decrease in protein content were obtained in the samples from the Dal Lake compared with those from Mansbal Lake (p<0.05). These data when compared with the values found in C. carpio and C. carassius from both the Dal Lake and Mansbal Lake kept under laboratory conditions after 15, 30, 45 and 60days of maintenance in clean media found that during depuration, all the enzyme activities came down significantly (p<0.05) indicating the compensatory response by the fish against the pesticide stress. Therefore, these parameters could be used as indicators of pesticide pollution in aquatic organisms and were recommended for environmental monitoring for investigating the mechanism involved in the recovery pattern.

A new tunable dispersive liquid-liquid micro extraction method developed for the simultaneous preconcentration of lead and cadmium from lakes water: a multivariate study

A green tunable dispersive liquid-liquid micro extraction (TDLLME) technique was established for the simultaneous enrichment of lead (Pb) and cadmium (Cd) from different lakes water before analysis by flame atomic absorption spectrometry (FAAS). A solvent known as tunable polarity solvent (TPS), mixture of 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1-decanol, has been employed as extractant in aqueous medium. In first step this mixture can be made polar by slowly bubbling the antisolvent trigger (CO2) through the solution, which makes a monophasic solution. During this step hydrophobic complexes of the metals with 8-hydroxy quinoline (8-HQ) were extracted by TPS. Then the mixture was switched back to hydrophobic one by heating and/or bubbling nitrogen, turning the mixture into two phases again. In second phase the metals were leached out from the complexes entrapped in TPS, by treating with a solution of nitric acid and exposing the mixture to CO2, which switched the mixture into single phase. Then N2 purging and/or heating again turned the mixture into two phases. The acidic aqueous phase containing the metals was introduced to FAAS for analysis, whereas TPS was recycled for next experiment. Different parameters, affecting the efficiency the technique, were optimized by multivariate approach. The method was applied to certified reference material of water and to a real sample spiked with standards of known concentration, to confirm its validity and accuracy. LOD obtained for Pb and Cd were 0.560 and 0.056μgL−1 respectively. The developed method was applied successfully to the real water samples of two lakes of Sindh, Pakistan.

A rapid, accurate and sensitive method with the new stable isotopic tags based on microwave-assisted dispersive liquid-liquid microextraction and its application to the determination of hydroxyl UV filters in environmental water samples

A rapid, accurate and sensitive method, using the stable isotope labeling (SIL), microwave-assisted dispersive liquid-liquid micro extraction (MADLLME) and the ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), was developed and validated for the determination of hydroxyl UV Filters in environmental water samples. A pair of new isotopic tags D0-/D3-1-methylindole-3-acetic acid (D0-/D3-MIAA) is synthesized, with which a simple yet efficient pretreatment MADLLME-SIL is developed. Under the optimized conditions (80℃, 240W, 180s), the sample pretreatment including analyte extraction, pre-concentration and isotope labeling can be finished conveniently in only 9min. D0-/D3-MIAA labeling improves the chromatographic retention by strengthening the hydrophobicity and enhances the MS response for 3–4 orders of magnitude. Excellent linearity is established by the H/D ratios of 1/10–10/1 with the correlation coefficients >0.9990. The quite low detection limits (0.54–1.79ng/L) are achieved, ensuring the trace detection. This method is successfully applied to a series of environmental water samples. The recoveries (93.2%~103.5%) are significantly improved and the analysis time is largely reduced (<15min). The excellent sensitivity, accuracy, recovery, and efficiency demonstrate this MADLLME-SIL-LC-MS/MS method a superior alternative for the analysis of UV filters in water samples.

Occurrence of Steroid Sex Hormone Progesterone in Influent and Effluent of Oxidation Pond and the River Outlet of Waste Water Treatment Case Study

Background and Objective: This studied about the occurrence of Endocrine Disrupting Compound (EDC) in interest of steroid sex hormone progesterone excretion in the environment, that focusing on water resource in terms of effluent and influent of the waste water treatment into the outlet river and environment. Materials and Methods: A method called dispersive liquid-liquid micro extraction with solidification of floating organic drop followed by High Performance Liquid Chromatography (HPLC) was used for determination of progesterone. The water sample was obtained through grab sample from the influent and effluent of waste water treatment-oxidation pond and the outlet river (Kalansanan river) where the effluent was discharged. Results: Based on the result obtained it is found that there were few detections and occurrences of steroid sex hormone progesterone in the study with detection range from lowest concentration of 4.278±7.411 ng mL–1 and the highest concentration recorded at 16.687±6.233 ng mL–1 and the average concentration of progesterone is at 6.356±3.112 ng mL–1. The highest detection of the progesterone was recorded in the effluent site sampling that indicates that the conventional treatment plant was not able to remove steroid sex hormone progesterone effectively and efficiently. Conclusion: From that point of the study, monitoring on the progesterone presence and status should be done due to the presence of progesterone even in nanogram per milliliter in environment bring and posed a life threat towards the living organism in the environment.

Ultrasound-assisted extraction combined with reverse phase-dispersive liquid-liquid micro extraction as a new approach for preconcentration and spectrophotometric determination of total phenol in marine sediments of Chabahar Bay

In this study, Reverse phase dispersive liquid–liquid micro extraction (RP-DLLME) technique have been successfully developed to preconcentrate trace amount of phenol from sediment samples as a prior step to its derivatization with 4-aminoantipyrine and enhanced determination by UV–Vis spectrophotometry after primary ultrasonic extraction. In this procedure, 50μL 0.7M NaOH solution was chosen as extraction solvent and other factors including pH, extraction time, concentration of 4-aminoantipyrine, type and volume of dispersive solvents were optimized. Under selected conditions, the limit of detection, the linearity range, relative standard deviation and enrichment factor of method were obtained 15μg·kg−1, 50–1800μg·kg−1, 4.8% (n=10) and 33, respectively. Finally, using the high sensitivity, low organic solvent consumption and waste generation method, total phenol content in marine sediments from several locations in Chabahar Bay (southeast Iran) was estimated at 55.8–73.2μg·kg−1.

Simultaneous Determination of 13 Priority Polycyclic Aromatic Hydrocarbons in Tehran's Tap Water and Water for Injection Samples Using Dispersive Liquid-Liquid Micro Extraction Method and Gas Chromatography-Mass Spectrometry.

Polycyclic aromatic hydrocarbons (PAHs) are classified as persistent and carcinogenic organic pollutants. PAHs contamination has been reported in water. Many of relevant regulatory bodies such as EU and EPA have regulated the limit levels for PAHs in drinking water. In this study, 13 priority polycyclic aromatic hydrocarbons (PAHs) were determined in tap water samples of Tehran and water for injection. Dispersive liquid-liquid microextraction procedure combined with gas chromatography-mass spectrometry was used for the extraction and determination of PAHs in the samples. Under the optimized conditions, the range of extraction recoveries and relative standard deviations (RSDs) of PAHs in water using internal standard (anthracene-d10) were in the range of 71-90% and 4-16%, respectively. Limit of detection for different PAHs were between 0.03 and 0.1 ngmL(-1). The concentration of PAHs in all tap water as well as water for injection samples were lower than the limit of quantification of PAHs. This is the first study addressing the occurrence of PAHs in water for injection samples in Iran using dispersive liquid-liquid micro extraction procedure combined with gas chromatography-mass spectrometry.

Preconcentration of uranium in water samples using dispersive liquid-liquid micro- extraction coupled with solid-phase extraction and determination with inductively coupled plasma-optical emission spectrometry

A new liquid phase microextraction method based on the dispersion of an extraction solvent into aqueous phase coupled with solid-phase extraction was investigated for the extraction, preconcentration and determination of uranium in water samples. 1-(2-Pyridylazo)-2-naphthol reagent (PAN) at pH 6.0 was used as a chelating agent prior to extraction. After concentration and purification of the samples in SPE C 18 sorbent, 1.5 mL elution sample containing 40.0 µL chlorobenzene was injected into the 5.0 mL pure water. After extraction and centrifuging, the sedimented phase was evaporated and the residue was dissolved in nitric acid (0.5 M) and was injected by injection valve into the ICP-OES. Some important extraction parameters, such as sample solution flow rate, sample pH, type and volume of extraction and disperser solvents as well as the salt addition were studied and optimized. Under the optimum conditions, the calibration graph was linear in the range of 0.5-500 µg L -1 . The detection limit was 0.1 µg L -1 . The relative standard deviation (RSD) at 5.0 µg L -1 concentration level was 6.6%. Finally, the developed method was successfully applied to the extraction and determination of uranium in the well, river, mineral, waste and tap water samples and satisfactory results were obtained. KEY WORDS : Dispersive liquid-liquid microextraction, Solid-phase extraction, Inductively coupled plasma-optical emission spectrometry, Uranium, Water samples Bull. Chem. Soc. Ethiop. 2015 , 29(3), 367-376. DOI: http://dx.doi.org/10.4314/bcse.v29i3.4

Determination of Cadmium in Rice by Dispersive Liquid-Liquid Micro Extraction-Hydride Generation-Atomic Fluorescence Spectrometry

Determination of Cadmium in Rice by Dispersive Liquid-Liquid Micro Extraction-Hydride Generation-Atomic Fluorescence Spectrometry

Investigation of the genotoxicity of endosulfan to freshwater Cyprinid fish Crucian carp (Carassius carassius L.) using the micronucleus and chromosomal aberration as biomarkers

This study was aimed to evaluate the in vivo genotoxic effects of endosulfan in freshwater fish crucian carp, Carassius carassius L. The LC50–96h value of endosulfan (with 95 % confidence limits), determined by probit analysis, was 0.070 (0.046–0.093) ppm L−1 and the estimated safe levels of endosulfan varied from 00.70 × 10−2 to 00.70 × 10−6 ppm L−1. Based on the LC50–96h value, three test concentrations (viz. sub-lethal I, II, and III) were determined to be 0.052, 0.035 and 0.017 ppm L−1, respectively, and the fish specimens were exposed to these concentrations for 35 days. The mean concentration of endosulfan in water samples (aquaria) was always within 5 % of the intended concentration when analyzed by dispersive liquid-liquid micro extraction (DLLME) followed by gas chromatography–mass spectrometry (GC-MS). Autopsy was done on days 1, 2, 3, 4, 7, 14, 21, 28 and 35 of endosulfan exposure for assessment of micronucleus (MN) formation and chromosomal aberrations (CA). The MN formation in the peripheral erythrocytes, authenticated by scanning electron microscopy (SEM), was found to be significantly higher (p < 0.05) in all the treated groups, including positive control cyclophosphamide (4 ppm L−1) compared to negative control. Similar significant effects (p < 0.05) were also observed on CA in the head kidney cells. In general, both MN and CA exhibited a concentration and time-dependent response. The current study revealed the potential genotoxicity of endosulfan in fish; and that the micronucleus and chromosomal assays are useful tools in determining genotoxicity of water pollutants and might be appropriate as a part of environmental monitoring program.