Cloud Point Extraction Efficiency Research Articles

Preconcentration and indirect quantification of trace nitrite, nitrate and total nitrite in selected beverage and milk samples using ion-pairing cloud-point extraction with acridine orange

A new indirect preconcentration method was developed for micellar-sensitive detection of trace nitrite as analyte by spectrophotometry. It is based on selective ion-pairing complex formation of triiodide ion, I3− with acridine orange, AOH+ (3,6-bis(dimethylamino) acridine) at pH 4.0 and its cloud-point extraction (CPE) with Triton X-114 as extracting agent. The extracted surfactant-rich phase is diluted with acetonitrile, and its absorbance is measured against analyte blank at 450 nm. The variables affecting CPE efficiency were investigated, and a set of optimized conditions was obtained. The calibration graph was rectilinear in the range of 1.5–150 μg L−1. The detection limit was 0.42 μg L−1 with a precision lower than 4.1%. The validation was statistically confirmed by analysis of a certified reference material. The method was successfully applied to determination of nitrite, nitrate and total nitrite in selected beverage and milk samples before and after reduction with two different reducing agents.

Phenol and benzenoid alcohols separation from aqueous stream using cloud point extraction: Scaling-up of the process in a mixer-settler

In the present work, the cloud point extraction (CPE) of three organic pollutants (phenol,benzyl alcohol and 1-phenylethanol) with aqueous solutions of biodegradable alkoxylated nonionic surfactants (TERGITOL 15-S-7 and SIMULSOL NW342), is investigated. First, the partial phase diagrams of the water–surfactant binary systems are established. Then, the effects of organic pollutants and sodium chloride on the cloud point (Tc) are determined. Extraction efficiency is evaluated by the following responses: percentage of solute extracted, E (%), residual concentrations of solute and surfactant in dilute phase (Xs,w, and Xt,w, respectively) and volume fraction of coacervate at equilibrium (ϕc). Three-dimensional empirical correlations are used for fitting the experimental results. The comparison between experimental and calculated values allows model parameter identification. Based on these data, CPE was implemented in a continuous mixer-settler device. The feasibility of a multi-stage crossflow process for the purification of samples containing phenol using SIMULSOL NW342 was tested. Six stages were required to reduce the pollutant concentration below the allowed level (0.3ppm), which proves the efficiency of CPE in the treatment of wastewaters.

Determination of strychnine, brucine, strychnine N-oxide, and brucine N-oxide in plasma samples after the oral administration of processed semen strychni extract by high-performance liquid chromatography with ultrasound-assisted mixed cloud point extraction.

A sensitive and efficient mixed cloud point extraction combined with high-performance liquid chromatography was developed for the simultaneous separation and determination of four alkaloids (strychnine, strychnine N-oxide, brucine, and brucine N-oxide) in plasma after the oral administration of processed semen strychni extract. Tergitol TMN-6 and cetyl-trimethyl ammonium bromide were chosen as the mixed surfactants, and ultrasound was employed to enhance the extraction efficiency. Some important parameters affecting the mixed cloud point extraction efficiency, such as the content of Tergitol TMN-6 and cetyl-trimethyl ammonium bromide, pH, salt effect, extraction temperature, and ultrasound time were studied and optimized. Under optimum conditions, the linear range of four alkaloids was from 1.0 to 1000 ng/mL. All correlation coefficients of the calibration curves were higher than 0.9993. The intraday and interday precision were below 8.65% and the limits of detection for the four alkaloids were less than 1.0 ng/mL (S/N = 3).

WITHDRAWN: Preconcentration and indirect quantification of trace nitrite, nitrate and total nitrite in selected beverage and milk samples using ion-pairing cloud-point extraction with acridine orange

Abstract A new indirect preconcentration method was developed for micellar-sensitive detection of trace nitrite as analyte by spectrophotometry. It is based on selective ion-pairing complex formation of triiodide ion, I3− with acridine orange, AOH+ (3,6-bis(dimethylamino) acridine) at pH 4.0 and its cloud-point extraction (CPE) with Triton X-114 as extracting agent. The extracted surfactant-rich phase is diluted with acetonitrile, and its absorbance is measured against analyte blank at 450 nm. The variables affecting CPE efficiency were investigated, and a set of optimized conditions was obtained. The calibration graph was rectilinear in the range of 1.5–150 μg L−1. The detection limit was 0.42 μg L−1 with a precision lower than 4.1%. The validation was statistically confirmed by analysis of a certified reference material. The method was successfully applied to determination of nitrite, nitrate and total nitrite in selected beverage and milk samples before and after reduction with two different reducing agents.

Determination of trace vanadium in sea cucumbers by ultrasound-assisted cloud point extraction and graphite furnace atomic absorption spectrometry

An ultrasound-assisted cloud point extraction (CPE) procedure was used for preconcentration and determination of vanadium by graphite furnace atomic absorption spectrometry. The vanadyl(IV) complex with ascorbic acid form a hydrophobic complex with 4-(2-pyridylazo) resorcinol (PAR) in a micelle medium, which is stable under our working conditions, and followed by its extraction into Triton X-100 surfactant-rich phase. The main factors affecting CPE efficiency, such as pH, concentrations of PAR, ascorbic acid and Triton X-100, incubation temperature, frequency and equilibration time of ultrasonic bath were investigated in detail. Under the optimum conditions, preconcentration of 10 mL sample gave a preconcentration factor of 36.4 and a detection limit of 4.0 µg kg−1. The proposed method was successfully applied to determination of vanadium in sea cucumbers with satisfactory results.

Determination of total Sn in some canned beverages by FAAS after separation and preconcentration

A micelle-mediated preconcentration method has been developed for determination of trace amounts of tin in canned beverage samples, which is widely used in food industry for packing, but its utilization is limited due to its toxic properties. The method is selectively based on the cloud point extraction (CPE) of Sn(IV) with Gallocyanin (GC+) and glycine as chelating agents in the mixed surfactant media, Polyethylene glycol sorbitan monolaurate (Tween 20) and Cetylpyridinium chloride (CPC) in Tris/HCl buffer, pH 8.5. The various variables affecting CPE efficiency were extensively optimized. Under the optimized conditions, the obtained calibration curve was highly linear in the range of 1–250μgL−1 for Sn(IV) with a good correlation coefficient of 0.9976. The detection limit of the method was 0.33μgL−1, and the relative standard deviations, RSDs, was in the range of 2.1–6.2% (25, 50 and 100μgL−1, N: 5). The matrix effect was also investigated. The method was successfully utilized for the determination of total Sn in some canned beverages by Flame Atomic Absorption Spectrometry (FAAS). Its validity was controlled by the analysis of two certified reference materials. It has been observed that the results are in agreement with the certified values.

Selective ligandless cloud point extraction of palladium from water and dust samples.

In this study, the phase-separation phenomenon of non-ionic surfactants was used for separation and preconcentration of Pd(II). The cloud point extraction (CPE) method is based on the formation of PdI2 which is then entrapped in the non-ionic surfactant Triton X-114. Ethanol acidified with 0.5 M HNO3 was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry. The main factors affecting CPE efficiency, such as sample solution pH, concentration of iodide ion and Triton X-114, equilibration temperature and time, were all investigated and optimized. At optimum conditions, a calibration curve was constructed for the determination of palladium according to the ligandless CPE procedure. Linearity was maintained between 1.0 to 500.0 ng/mL. The LOD based on three times the SD of the blank divided by the slope of analytical curve, (3Sb/m) was 0.3 ng/mL. Seven replicate determinations of a solution containing of 4.0 μg palladium gave a mean absorbance of 0.359 with RSD±1.85%. The high efficiency of CPE to carry out the determination of palladium in complex matrixes was demonstrated. The proposed method has been applied to the determination of trace amounts of palladium in a platinum-iridium alloy, water, and dust samples, with satisfactory results.

Ion-pair cloud-point extraction: a new method for the determination of water-soluble vitamins in plasma and urine.

A novel, simple, and effective ion-pair cloud-point extraction coupled with a gradient high-performance liquid chromatography method was developed for determination of thiamine (vitamin B1 ), niacinamide (vitamin B3 ), pyridoxine (vitamin B6 ), and riboflavin (vitamin B2 ) in plasma and urine samples. The extraction and separation of vitamins were achieved based on an ion-pair formation approach between these ionizable analytes and 1-heptanesulfonic acid sodium salt as an ion-pairing agent. Influential variables on the ion-pair cloud-point extraction efficiency, such as the ion-pairing agent concentration, ionic strength, pH, volume of Triton X-100, extraction temperature, and incubation time have been fully evaluated and optimized. Water-soluble vitamins were successfully extracted by 1-heptanesulfonic acid sodium salt (0.2% w/v) as ion-pairing agent with Triton X-100 (4% w/v) as surfactant phase at 50°C for 10 min. The calibration curves showed good linearity (r(2) > 0.9916) and precision in the concentration ranges of 1-50 μg/mL for thiamine and niacinamide, 5-100 μg/mL for pyridoxine, and 0.5-20 μg/mL for riboflavin. The recoveries were in the range of 78.0-88.0% with relative standard deviations ranging from 6.2 to 8.2%.

Evaluation of a cloud point extraction approach for the preconcentration and quantification of trace CuO nanoparticles in environmental waters

The cloud point extraction (CPE) of commercial copper(II) oxide nanoparticles (CuO NPs, mean diameter of 28nm) in water samples was fully investigated. Factors such as Triton X-114 (TX-114) concentration, pH, incubation temperature and time, were optimized. The effects of CuO NP behavior like agglomeration, dissolution, and surface adsorption of natural organic matter, Cu2+, and coating chemicals, on its recovery were studied. The results indicated that all the CPE factors had significant effects on the extraction efficiency. An enrichment factor of ∼89 was obtained under optimum CPE conditions. The hydrodynamic diameter of CuO NPs increased to 4–5μm upon agglomeration of NP-micelle assemblies, and decreased at pH >10.0 at which the extraction efficiency was also lowered. The solubility and therefore, the loss of NPs were greatly enhanced at pH <8.5 and in the first 60min of incubation, whereas it declined at elevated incubation temperatures. Our results showed that the dissolved organic carbon (DOC) >5mgCL−1 and Cu2+ >2 times that of CuO NPs, lowered and enhanced the extraction efficiency, respectively. Pre-treatment of samples with 3% wv−1 of hydrogen peroxide and 10mM of ethylenediaminetetraacetic acid minimized the interferences posed by DOC and Cu2+, respectively. The decrease in CPE efficiency was also evident for ligands like poly(ethylene glycol). The TX-114-rich phase could be determined with either inductively coupled plasma mass spectrometry following microwave digestion, or graphite furnace atomic absorption spectrometry. The detection limits for CuO NPs were 0.02 and 0.06μgL−1 using these techniques, respectively. The optimum sample pre-treatment and CPE conditions were successfully applied to the river and wastewater samples. The relative recoveries of CuO NPs spiked at 5–100μgL−1 (as Cu) in these samples were in the range of between 59.2 and 108.2%. The approach demonstrates a robust analytical method for detecting trace levels of CuO NPs at their original states and assessing their exposure risks in real aquatic environments.

Determination of Trace Inorganic Mercury Species in Water Samples by Cloud Point Extraction and UV-Vis Spectrophotometry

A new micelle-mediated extraction method was developed for preconcentration of ultratrace Hg(II) ions prior to spectrophotometric determination. 2-(2'-Thiazolylazo)-p-cresol (TAC) and Ponpe 7.5 were used as the chelating agent and nonionic surfactant, respectively. Hg(II) ions form a hydrophobic complex with TAC in a micelle medium. The main factors affecting cloud point extraction efficiency, such as pH of the medium, concentrations of TAC and Ponpe 7.5, and equilibration temperature and time, were investigated in detail. An overall preconcentration factor of 33.3 was obtained upon preconcentration of a 50 mL sample. The LOD obtained under the optimal conditions was 0.86 microg/L, and the RSD for five replicate measurements of 100 microg/L Hg(II) was 3.12%. The method was successfully applied to the determination of Hg in environmental water samples.

Determination of Trace Cd in Alcoholic and Nonalcoholic Beverages by Coupling Cloud Point Extraction with Spectrophotometry

A cloud-point extraction (CPE) process using the nonionic surfactant, Triton X-114 to extract Cd(II) ions from aqueous solutions was investigated. The method is based on the ion-pairing reaction of Cd(II) with Victoria blue B (VBB+) in presence of excess iodide at pH 4.0 and extraction of the complex formed. The chemical variables affecting CPE efficiency were studied, and the analytical characteristics of the method were obtained. The calibration curves were obtained in the ranges of 1.0–30 and 10–500 µg/L for Cd(II) ion with the detection limits of 0.34 and 3.8 µg/L at 608 and 634 nm, respectively. The selectivity study was also tested. The precision (N: 5, 25 µg/L) was 2.85% relative standard deviation. The results obtained for two certified reference samples were in a good agreement with the certified values. The method was successfully applied to the determination of Cd(II) in beverage samples.

Influence of Particle Coating and Matrix Constituents on the Cloud Point Extraction Efficiency of Silver Nanoparticles (Ag-NPs) and Application for Monitoring the Formation of Ag-NPs from Ag+

For the quantification of silver nanoparticles (Ag-NPs) in environmental samples using cloud point extraction (CPE) for selective enrichment, surface modification of the Ag-NPs and matrix effects can play a key role. In this work we validate CPE with respect to the influence of different coatings and naturally occurring matrix components. The Ag-NPs tested were functionalized with inorganic and organic compounds as well as with biomolecules. Commercially available NPs and NPs synthesized according to methods published in the literature were used. We found that CPE can extract almost all Ag-NPs tested with very good efficiencies (82-105%). Only Ag-NPs functionalized with BSA (bovine serum albumin), which is a protein with the function to keep colloids in solution, cannot be extracted. No or little effect of environmentally relevant salts, organic matter, and inorganic colloids on the CPE of AgNPs was found. Additionally we used CPE to observe the in situ formation of Ag-NPs produced by the reduction of Ag(+) with natural organic matter (NOM).

A fast and reliable method for quantitative determination of total mercury in vegetables

A cloud-point extraction (CPE) process using the nonionic surfactant, polyethylene glycol tert octylphenyl ether (Triton X-114) was employed for determination of Hg(II) ions in aqueous solutions. The method is based on the ion-pairing reaction of Hg(II) with Pyronin B (PyrB+) in the presence of excess iodide at pH 6.0 and extraction of the complex formed. The chemical variables affecting CPE efficiency were studied, and the analytical characteristics of the method were obtained. The calibration curves were linear in the range of 1–40 μg L−1 with the detection limits of 0.35 and 0.30 μg L−1 at 556 and 521 nm. Selectivity was also tested. The coefficients of variation of the method are 2.4% and 5.2% for five replicate measurements of mercury at levels of 10 and 25 μg L−1, respectively. The results obtained for two certified reference samples were in a good agreement with the certified values. The method was applied to the determination of total mercury in vegetable samples.

Toward a robust analytical method for separating trace levels of nano-materials in natural waters: cloud point extraction of nano-copper(II) oxide

Cloud point extraction (CPE) factors, namely Triton X-114 (TX-114) concentration, pH, ionic strength, incubation time, and temperature, were optimized for the separation of nano-sized copper(II) oxide (nCuO) in aqueous matrices. The kinetics of phase transfer was studied using UV-visible spectroscopy. From the highest separation rate, the most favorable conditions were observed with 0.2 % w/v of TX-114, pH = 9.0, ionic strength of 10 mM NaCl, and incubation at 40 °C for 60 min, yielding an extraction efficiency of 89.2 ± 3.9 % and a preconcentration factor of 86. The aggregate size distribution confirmed the formation of very large nCuO-micelle assemblies (11.9 μm) under these conditions. The surface charge of nCuO was also diminished effectively. An extraction efficiency of 91 % was achieved with a mixture of TX-100 and TX-114 containing 30 wt.% of TX-100. Natural organic and particulate matters, represented by humic acid (30 mg/L) and micron-sized silica particles (50 mg/L), respectively, did not significantly reduce the CPE efficiency (<10 %). The recovery of copper(II) ions (20 mg/L) in the presence of humic acid was low (3-10 %). The spiked natural water samples were analyzed either directly or after CPE by inductively coupled plasma mass spectrometry following acid digestion/microwave irradiation. The results indicated the influence of matrix effects and their reduction by CPE. A delay between spiking nCuO and CPE may also influence the recovery of nCuO due to aggregation and dissolution. A detection limit of 0.04 μg Cu/L was achieved for nCuO.

A reliable method of quantification of trace copper in beverages with and without alcohol by spectrophotometry after cloud point extraction

A new cloud point extraction (CPE) method was developed for the separation and preconcentration of copper (II) prior to spectrophotometric analysis. For this purpose, 1-(2,4-dimethylphenyl) azonapthalen-2-ol (Sudan II) was used as a chelating agent and the solution pH was adjusted to 10.0 with borate buffer. Polyethylene glycol tert-octylphenyl ether (Triton X-114) was used as an extracting agent in the presence of sodium dodecylsulphate (SDS). After phase separation, based on the cloud point of the mixture, the surfactant-rich phase was diluted with acetone, and the enriched analyte was spectrophotometrically determined at 537 nm. The variables affecting CPE efficiency were optimized. The calibration curve was linear within the range 0.285-20 µg L-1 with a detection limit of 0.085 µg L-1. The method was successfully applied to the quantification of copper in different beverage samples.

A Green Method Using a Micellar System for Determination of Andrographolide and Dehydroandrographolide in Human Plasma

A method based on cloud point extraction (CPE) coupled with high-performance liquid chromatography separation and ultraviolet (UV) detection was developed to determine andrographolide and dehydroandrographolide in human plasma. The nonionic surfactant Triton X-114 was chosen as the extraction medium. Variable parameters affecting the CPE efficiency were evaluated and optimized, such as concentrations of Triton X-114 and NaCl, pH, equilibration temperature and equilibration time. A Zorbax SB C18 column (250 × 4.6 mm i.d., 5 µm) was used for separation of the two analytes at 30°C. The UV detection was performed at 254 nm. Under the optimum conditions, the limits of detection of andrographolide and dehydroandrographolide are 0.032 and 0.019 µg/mL, respectively. The intra-day and inter-day precisions expressed as relative standard deviation ranged from 3.2 to 7.3% and from 2.9 and 8.6%. The recoveries of andrographolide and dehydroandrographolide were in the range of 76.8-98.6% at three fortified concentrations of 0.1, 0.5 and 1.0 µg/mL. This method was efficient, environmentally friendly, rapid and inexpensive for the extraction and determination of andrographolide and dehydroandrographolide in human plasma.

Development of a cloud point extraction method for the determination of phenolic compounds in environmental water samples coupled with high‐performance liquid chromatography

A method based on ultrasound-assisted cloud point extraction (CPE) was developed for the determination of phenolic compounds in water samples by high-performance liquid chromatography coupled with diode array detection (DAD) (HPLC-DAD). A nonionic surfactant, Tergitol 15-S-7, was chosen as the surfactant. The parameters affecting the CPE efficiency, such as Tergitol 15-S-7 concentration, salt concentration, extraction temperature, incubation time, centrifugation time, ultrasonic time, sample pH, and dilution solvent were systematically evaluated and optimized. Under the optimum experimental conditions, the linear regression coefficients of the standard curves were greater than 0.9986 and the limits of detection were in the range of 1.7-6.0 μg/L. The method was shown to be reproducible and reliable with intraday and interday relative standard deviations lower than 4.0 and 5.8%, respectively. The recoveries for the addition of different concentrations of phenolic compounds to water samples were in the range of 81.1-109.4%.

Cloud‐point extraction combined with HPLC for determination of larotaxel in rat plasma: A pharmacokinetic study of liposome formulation

A simple and efficient method based on cloud-point extraction combined with high-performance liquid chromatography was developed and validated for the determination of larotaxel in rat plasma. Nonionic surfactant Triton X-114 was chosen as the extraction solvent. Variable parameters affecting the cloud-point extraction efficiency, for example the nature and concentration of surfactant, NaOH concentration, incubation temperature, and time were evaluated and optimized. Chromatographic separation was accomplished on a Diamonsil C(18) column (150 mm × 4.6 mm, 5 μm) using a mobile phase consisting of acetonitrile and 0.1% phosphoric acid with pH 4.0 (60:40, v/v). The calibration curve showed good linearity over the range of 0.05-10 μg/mL. Under the optimum conditions, the method was shown to be reproducible and reliable with intraday precision below 5.7%, interday precision below 7.2%, accuracy within ±3.5%, and mean extraction recovery of 91.8-94.2%. The validated method was successfully applied to the pharmacokinetic study of larotaxel in rat plasma after a single intravenous administration of larotaxel injection and larotaxel-loaded liposome, respectively. The results indicated that the larotaxel-loaded liposome led to significant differences in pharmacokinetic profile.

USING AN INDOL DERIVATIVE AS COMPLEXING AGENT FOR CLOUD POINT PRECONCENTRATION AND DETERMINATION OF MAGNESIUM AND SILVER IONS IN VARIOUS SAMPLES BY FAAS

A very simple cloud point extraction (CPE) methodology for the preconcentration of trace amounts of silver and magnesium as a prior step for their determination by flame atomic absorption spectrometry (FAAS) has been developed. The method is based on the extraction of silver and magnesium at pH 10 by using non-ionic surfactant Triton X-114 and 4 methyl-3-((1-H-Indol-3-iyl) (phenyl) methyl)) -1-H-Indol (MPBIM) as a complexing agent. Several important variables that affect the CPE efficiency and FAAS signal were investigated and optimized. The calibration curves, using the preconcentration system, were linear in the range of 0.007-0.200 μg mL-1 with a correlation coefficient of 0.999. The lower limits of detection (3s) obtained in the optimal conditions were 1.47 ng mL-1 and 3.00 ng mL-1 for Mg2+ and Ag+ ions, respectively. The relative standard deviation for five replicate determinations of magnesium and silver at 0.133 μg mL-1 concentration level, were 1.17 and 0.97, respectively. The proposed method was successfully applied to the ultra-trace determination of silver and magnesium in various water samples, blood serum, urine, and radiology film samples.

Cloud point extraction combined with graphite furnace atomic absorption spectrometry for speciation of Cr(III) in human serum samples

A cloud point extraction (CPE) method for the preconcentration of ultra-trace chromium speciation in human serum samples prior to determination by graphite furnace atomic absorption spectrometry (GFAAS) had been developed in this paper. In this method, Cr(III) reacts with 1-(2-pyridylazo)-2-naphthol (PAN) yielding a hydrophobic complex, which is then entrapped in the surfactant-rich phase, whereas Cr(VI) remained in aqueous phase. Thus, separation of Cr(III) and Cr(VI) could be realized. Total chromium was determined after the reduction of Cr(VI) to Cr(III) by using ascorbic acid as reducing reagent. PAN was used not only as chelating reagent in CPE, but also as chemical modifier in GFAAS. Triton X-114 non-ionic surfactant had been used as an extraction medium. The main factors affecting CPE efficiency, such as pH of solution, concentration and kind of complexing agent, concentration of non-ionic surfactant, equilibration temperature and time, were investigated in detail. An enrichment factor of 83.5 was obtained for the preconcentration of Cr(III) with 10 mL solution. Under the optimal conditions, the detection limit of Cr(III) was 0.02 μg L −1. The relative standard deviation was 2.6% for intra-day assay precision ( n = 7, c = 10 ng mL −1), values of recovery for chromium were from 92.0% to 94.7% for three samples. This method is simple, accurate, and sensitive and can be applied to determine ultra-trace chromium speciation in human serum.