Determination of chromium in foodstuffs by using novel adsorbent in vortex assisted-dispersive solid phase micro-extraction method: An application of multivariate techniques.

A new graft copolymer composed of polystyrene and polylinoleic acid (PLinas) with the sodium salt of iminodiacetate (Ida) was synthesized and used as an adsorbent. The vortex-assisted dispersive solid-phase micro-extraction (VA-dSPµE) method was used for the extraction and pre-concentration of chromium. Multivariate methodologies, such as factorial design and 3D surface plots, were applied for screening and optimizing effective extraction parameters. The influence of diverse analytical parameters, such as pH, sample volume, and interfering ions, on the extraction of chromium was studied. The calibration standard curve exhibited a linear range from 0.01 to 0.50 µg L-1. The relative standard deviation and limit of detection were found to be 1.65 % and 0.003 µg L-1, respectively. Extraction recoveries were found in the range of 96 to 99 % by using certified reference materials (CRMs). The adsorbent capacity of PLinas-Ida was found to be 112 mg g-1. The VA-dSPµE method demonstrated its effectiveness in the pre-concentration and determination of chromium within samples of foodstuffs by graphite furnace-atomic absorption spectrometry (GF-AAS).

Ultra-Sensitive Determination of Cadmium in Food and Water by Flame-AAS after a New Polyvinyl Benzyl Xanthate as an Adsorbent Based Vortex Assisted Dispersive Solid-Phase Microextraction: Multivariate Optimization.

Background: Cadmium (Cd) is a very toxic and carcinogenic heavy metal even at low levels and it is naturally present in water as well as in food. Methods: A new polyvinyl benzyl xanthate (PvbXa) was synthesized and used as a new adsorbent in this work. It contains pendant sulfide groups on the main polystyryl chain. Using this new adsorbent, PvbXa, a vortex-assisted dispersive solid-phase microextraction (VA-dSPµE) procedure was developed for the determination of cadmium from food and water samples via flame atomic absorption spectrophotometry (FAAS). Synthesized PvbXa was characterized by 1H Nuclear magnetic resonance (NMR) Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), and X-ray Photoelectron Spectroscopy (XPS). The different parameters of pH, sample volume, mixing type and time, sorbent amount, and eluent time were optimized using standard analytical methods. Results: The optimized method for assessment of Cd in food and water samples shows good reliability. The optimum conditions were found to be a 0.20-150 µg L-1 linear range, 0.06 µg L-1 LOD, 0.20 µg L-1 LOQ, 4.3 RSD %, and a preconcentration factor of 160. Conclusions: The statistically experimental variables were utilized using a central composite design (CCD). The present method is a low-cost, simple, sensitive, and very effective tool for the recovery of Cd.

Development of homogeneous dispersive solid phase extraction using albumin as a green sorbent and its combination with dispersive liquid-liquid microextraction: application in extraction of pesticides from fruit juices.

In the current study, salt- and pH-induced homogeneous dispersive solid phase extraction was developed using albumin as a sorbent for the extraction of some pesticides (diazinon, diniconazole, haloxyfop-R-methyl, and hexaconazole) from fruit juice of orange, pomegranate, and barberry. The extracted analytes were more concentrated by dispersive liquid-liquid microextraction to obtain high enrichment factors and low detection limits prior to their determination by gas chromatography-mass spectrometry. In the extraction process, human serum albumin solution was added to the sample solution at the µL-level and a homogeneous solution was obtained. Then, albumin was precipitated into the solution by adding an inorganic salt and decreasing the solution pH. By doing so, the analytes were adsorbed by albumin effectively due to their high adsorption capacity and large surface area. Following this, the pesticides were eluted from the albumin sorbent using an elution solvent and used in a dispersive liquid-liquid microextraction step. Under the optimum extraction conditions, low limits of detection and quantification were achieved in the ranges of 0.02-0.04 and 0.07-0.13 ng mL-1, respectively. The calibration curves were linear in the range of 0.13-250 ng mL-1. Relative standard deviation as a criterion for precision and the method repeatability were in the ranges of 2.9-4.2% for intra- (n = 5, C = 5 or 50 ng mL-1) and 3.2-5.2% for inter-day (n = 5, 50 ng mL-1) precisions. The enrichment factors and extraction recoveries were in the ranges of 390-460 and 78-92%, respectively. Finally, the offered procedure was applied for the analysis of pesticide residues in some fruit juice samples.

Novel silver-morphine-functionalized polypropylene (AgPP-mrp) nanocomposite for the degradation of dye removal by multivariate optimization approach.

As a novel adsorbent, an opioid silver-morphine-functionalized polypropylene was synthesized through a one-pot reaction at room temperature and successfully used for the simple one-pot photocatalytic degradation catalyst of methyl orange removal from wastewater. UV spectral analysis reveals a special reference to the excitation of surface plasmon resonance as the main characteristic of the polymer-Ag nanocomposite in toluene solution peak at 420 nm in AgPP-mrp catalyst. The 1H NMR spectrum showed no sign of Ag NP peaks revealing small size distribution in the channels of morphine-functionalized polypropylene polymer. The morphology of silver nanoparticle-doped polymer through scanning electron microscopy (SEM-EDX) reveals PP-mrp with continuous matrix and Ag NPs (0.87 wt%). Furthermore, photocatalytic degradation of methyl orange was investigated on AgPP-mrp catalyst spectrophotometrically under solar irradiation in waste effluent, demonstrating high degradation efficiency. According to experimental findings, silver nanoparticles (AgPP-mrp) achieved high degradation capacities of 139 mg/g equivalent to 97.4% of photodegradation in a little period of time (35 min), as associated with previously stated materials and follow pseudo-second-order kinetic degradation tail of a high regression coefficient (R2 = 0.992). The suggested techniques offer a linear reaction for MO over the pH range of 1.5 to 5 and a degradation temperature of 25 to 60 °C. Central composite design and response surface methodology statistics recommend pH of the reaction medium and time as important variables for methyl orange degradation on AgPP-mrp photocatalytic. AgPP-mrp on the photocatalytic phenomenon based on heterojunction catalytic design producing electron holes (e-), as well as superoxides for the successful degradation of methyl orange.

Ultrasound assisted dispersive solid phase microextraction using polystyrene-polyoleic acid graft copolymer for determination of Sb(III) in various bottled beverages by HGAAS.

A new polyoleic acid-polystyrene (PoleS) block/graft copolymer was synthesized and applied as adsorbent for ultrasound assisted dispersive solid phase microextraction (UA-DSPME) of Sb(III) in different bottled beverages and analysis using hydride generation atomic absorption spectrometry (HGAAS). Adsorption capacity of the PoleS was 150 mg g-1. Several sample preparation parameters such as sorbent amount, solvent type, pH, sample volume and shaking time were optimized (based on central composite design (CCD) approach) and evaluated in respect to the recovery of Sb(III). The method revealed a high tolerance limit of matrix ions presence. Under optimized conditions, linearity range, the limit of detection, the limit of quantitation, extraction recovery, enhancement factor, preconcentration factor were 5-800 ng L-1, 1.5 ng L-1, 5.0 ng L-1, 96%, 82, 90, respectively. Accuracy of the UA-DSPME method was confirmed based on different certified reference materials and standard addition method. Factorial design was utilized to estimate the influences of variables of recovery of Sb(III).

Liquid Phase Microextraction of Hazardous Compounds in Dairy Products; Principal and Practical Aspects.

Liquid phase microextraction techniques are considered as the miniaturized version of traditional liquid-liquid extraction, which use only several microliters of a proper solvent to extract the analytes from sample. In these methods, the target analytes are migrated into a water-immiscible organic solvent (acceptor phase) from an aqueous sample (donor phase). They are mainly classified into three main groups including (a) single-drop microextraction, (b) dispersive liquid-liquid microextraction, and (c) hollow fiber-liquid phase microextraction. These techniques have been successfully applied to the assessment of different analytes in food samples, pharmaceuticals, beverages, and so on. This review mainly focuses on up-to-date information on the application of liquid phase microextraction techniques in dairy products. The advantages and disadvantages of the developed liquid phase microextraction methods were discussed.

Application of Recently used Green Solvents in Sample Preparation Techniques: A Comprehensive Review of Existing Trends, Challenges, and Future Opportunities.

Green solvents (GSs) has gained significant attention in recent years due to their potential as safer and more sustainable alternatives to traditional organic solvents. Solvents are used in a wide range of applications, from industrial processes to everyday products. Solvent emissions and losses can have a significant impact on the environment and human health, which is why many initiatives are being undertaken to get rid of or switch to eco-friendly alternatives. A key area of green chemistry that led to the concept of "green" solvents is the development of alternative solvents that are less toxic and more environmentally friendly than traditional organic solvents. The advantages of using green solvents over conventional ones are their environmental friendliness, biocompatibility, biodegradability, and simplicity of preparation. Different sample preparation techniques have successfully utilized green solvents to offer a sustainable separation media for the extraction of a variety of inorganic and organic compounds which are crucial for research in environmental samples. Recent developments in green analytical chemistry (GAC) have focused on how to prepare and use samples using environmentally sustainable solvents. The current study covers the advance and currently used green solvents with an emphasis on environmentally friendly sample preparation methods. This review aims to briefly summarize the current state of knowledge about the use of green solvents particularly ionic liquids, deep eutectic solvents and switchable solvents (SSs) with the perspective of GAC in sample preparation methods.

Development of a Sensitive Method for Cadmium Determination in Fish Tissue and Drinking Water Samples by FAAS Using SQT In Situ Atom Trapping.

A sensitive and robust trap method was developed for the determination of cadmium (Cd) by using a slotted quartz tube. Using this method at a sample suction rate of 7.4 mL/min for 4.0 min collection, a 1467-fold increase in sensitivity was obtained compared to the flame atomic absorption spectrometry method. Under the optimized conditions, a limit of detection of 0.075 ng mL-1 was obtained for the trap method. The interference effects of hydride-forming elements, transition metals, and some anions on the Cd signal were investigated. The developed method was evaluated by analyzing "Sewage Sludge-industrial origin (BCR no: 146R)", "NIST SRM 1640a Trace elements in natural water", and "DOLT: 5 Dogfish Liver". There was a good agreement between the certified and found values at the 95% confidence level. This method was applied successfully for the determination of Cd in drinking water and some fish tissue samples (liver, muscle, and gill) obtained from Mugla province.

Preparation of fatty acid-based ternary deep eutectic solvents: Application for determination of tetracycline residue in water, honey and milk samples by using vortex-assisted microextraction.

Simple, rapid, low cost, selective, and sensitive analytical method was developed using fatty acid-based ternary deep eutectic solvents (TDESs) for extraction and determination of tetracycline in honey, milk and water samples by vortex assisted (VA) microextraction and UV-vis spectrophotometer. Four different TDES were prepared by combination of nonanoic acid, dodecanoic acid, decanoic, hexanoic acid, octanoic acid. Analytical parameters such as pH, TDES types and its molar ratio, dispersive solvent types and solvent volume and salt effect were optimized. VA-TDES method was good recovery of tetracycline in the samples from 94 to 99%. The LOD and LOQ values were found 1.0 and 3.3 µg L-1, respectively. The linear range of calibration graph was 3.3 -450 µg L-1. Intra-day and inter-day precision was found 2.8-4.1% and 3.6-5.2%. Enhancement factor was found 109. The factorial design was drawn to evaluate the significant level of factors and effects of variables on the recovery of tetracycline. Standard addition method was used for the validation and accuracy of the method. Present VA-TDES method was successfully applied to real samples.

A critical review of selected preconcentration techniques used for selenium determination in analytical samples.

Selenium (Se) is considered to be an essential trace element needed for all living organisms. The importance, deficiency, and toxic effects of Se mainly depend on its quantity and chemical nature. It has been observed that the inorganic versions of Se are more hazardous than the organic versions. This review is mainly focused on the application of different extraction methods used for Se extraction and determination such as microextraction, solid-phase extraction (SPE), and their modified modes in the last 12 years. The use of different dispersive medium (magnetic field, ultrasonic radiation, and vortex agitator) to enhance Se separation is also part of this review. The usage of environmentally friendly solvents such as supramolecular solvents, hydrophobic deep eutectic solvents (DESs), and ionic liquids (ILs) are also the focus of attention in this review. This review is also emphasized the application of advanced microextraction methods, particularly liquid-phase microextraction (LPME). The most recent advances in LPME extraction techniques for Se in various environmental samples, as well as their prospects, are reviewed. Additionally, a summary of cheap, simple, and accurate techniques that have not yet been used to determine small amounts of Se has been provided.

A New Trend and Future Perspectives of the Miniaturization of Conventional Extraction Methods for Elemental Analysis in Different Real Samples: A Review.

Sample preparation is one of the viable procedures to be used before analysis to enhance sensitivity and reduce the matrix effect. The current review is mainly emphasized the latest outcome and applications of microextraction techniques based on the miniaturization of the classical conventional methods based on liquid-phase and solid-phase extraction for the quantitative elemental analysis in different real samples. The limitation of the conventional sample preparation methods (liquid and solid phase extraction) has been overcome by developing a new way of reducing size as compared with the conventional system through the miniaturization approach. Miniaturization of the sample preparation techniques has received extensive attention due to its extraction at microlevels, speedy, economical, eco-friendly, and high extraction capability. The growing demand for speedy, economically feasible, and environmentally sound analytical approaches is the main intention to upgrade the conventional procedures apply for sample preparation in environmental investigation. A growing trend of research has been perceived to quantify the trace for elemental analysis in different natures of real samples. This review also recapitulates the current futuristic scenarios for the green and economically viable procedure with special overemphasis and concentrates on eco-friendly miniaturized sample-preparation techniques such as liquid-phase microextraction (LPME) and solid-phase microextraction (SPME). This review also emphasizes the latest progress and applications of the LPME and SPME approach and their future perspective.

Ultrasonic-assisted dispersive liquid-liquid microextraction based on hydrophilic deep eutectic solvents: Application to lead and cadmium monitoring in water and food samples.

A green and innovative ultrasonic-assisted dispersive liquid-liquid microextraction using hydrophilic deep eutectic solvents (UA-HDES-DLLME) was developed for the selective and simultaneous extraction and enrichment of Pb (II) and Cd (II) in water and food samples for flame atomic absorption spectrometry. Several natural deep eutectic solvents (NADES) were used for the preparation of six different HDES and methyl violet was used as chelating reagent. Effective parameters such as pH, sonication time, methyl violet amount, DES type, dispersive solvent types, etc were optimized. Relative standard deviation (RSD) and preconcentration factor (PF) were 4.0% and 80. Low limits of detection (LOD, 1.3 ng mL-1 for Pb (II) and 0.33 ng mL-1 for Cd (II)) and quantification (LOQ, 4.0 ng mL-1 for Pb (II) and 1.0 ng mL-1 for Cd (II)) were found. The method accuracy was confirmed with analyses of certified reference materials.

Deep Eutectic Solvents for Extraction and Preconcentration of Organic and Inorganic Species in Water and Food Samples: A Review.

Deep eutectic solvents (DESs) have been developed as green solvents and these are capable as alternatives to conventional solvents used for the extraction of organic and inorganic species from food and water samples. The continuous generation of contaminated waste and increasing concern for the human health and environment have compelled the scientific community to investigate more ecological schemes. In this concern, the use of DESs have developed in one of the chief approach in the field of chemistry. These solvents have appeared as a capable substitute to conventional hazardous solvents and ionic liquids. The DESs has distinctive properties, easy preparation and components availability. It is not only used in scienctific fields but also used in quotidian life. There are many advantages of DESs in analytical chemistry, they are largely used for extraction and determination of inorganic and organic compounds from different samples. In previous a few years, several advanced researches have been focused on the separation and preconcentration of low level of pollutants using DESs as the extractants. This review summarizes the use of DESs in the separation and preconcentration of organic and inorganic species from water and food samples using various microextraction processes.

Synthesized of poly(vinyl benzyl dithiocarbonate-dimethyl amino ethyl methacrylate) block copolymer as adsorbent for the vortex-assisted dispersive solid phase microextraction of patulin from apple products and dried fruits.

A new and novel poly(vinyl benzyl dithiocarbonate-dimethyl amino ethyl methacrylate) block copolymer (Pvb-DMA-Xa) as adsorbent was synthesized for the vortex-assisted dispersive solid phase microextraction (VA-DSPME) of patulin from apple products and dried fruits using Uv-visible spectrophotometer. The characterization of synthesized Pvb-DMA-Xa block copolymer was performed with Fourier Transform Infrared spectroscopy (FTIR-ATR) technique. Analytical characteristics such as pH, sorbent amount, adsorption time, eluent type and its volume, desorption time and adsorption capacity were optimized. Limit of detection (3Sb/m) and limit of quantitation (10Sb/m) were found 0.3 and 1.0 ng mL-1. Linear dynamic range (LDR), relative standard deviation (RSD) and recovery values were found in the range of 1-30 ng mL-1, 2.1-2.7 % and 93.5-97.3 %, respectively. Enhancement factor (EF) was found 193. The accuracy of the method was confirmed with standard addition method and analyzing of samples by reference method.

Synthesized of a novel xanthate functionalized polypropylene as adsorbent for dispersive solid phase microextraction of caffeine using orbital shaker in mixed beverage matrices.

A newly synthesized xanthate functionalized chlorinated polypropylene (PP-Xa) was used as adsorbent for the orbital shaker based on dispersive solid phase microextraction (OS-DSPME) of caffein from several tea, coffee, energy drink, coca-cola and chocolate samples using UV-vis. spectrophotometer. Synthesized PP-Xa was characterized using Fourier Transform Infrared spectroscopy (FTIR-ATR) and nuclear magnetic resonance spectroscopy (1H NMR). Various parameters like pH, PP-Xa amount, extraction time, type of eluent and its volume were optimized. Linear range, detection limit (LOD), limit of quantification (LOQ), relative standard deviation (RSD), recovery values, and enrichment factor (EF) were found 90-1000 µgL-1, 27.3 µg L-1, 90 µg L-1, 1.9-2.6%, 98 ± 2%, and 167, respectively. Adsorption capacity of PP-Xa was found 271.9 mg g-1. Standard addition and reference method were used for confirm the accuracy of present method.

In-situ sorbent formation for the extraction of pesticides from honey.

An organic polymer was re-precipitated in solution to use as an adsorbent in dispersive solid-phase extraction of some pesticides from honey samples prior to their determination by high-performance liquid chromatography-tandem mass spectrometry. In this approach, different deep eutectic solvents were prepared using lysine and their ability in elution of the analytes from the adsorbent surface was tested. A diluted honey solution was transferred into a glass test tube and then a solution of polystyrene dissolved in dimethylformamide was injected into the solution. By doing this, polystyrene is re-precipitated in the solution and dispersed in whole parts of it as many tiny particles. Then the mixture was centrifuged and the adsorbed analytes on the particles were eluted using a proper hydrophilic deep eutectic solvent. The central composite design approach was used for the optimization of effective parameters. The limits of detection and quantification were in the ranges of 0.06-0.20 and 0.22-0.69 ng/g, respectively. The calibration curves obtained by matrix-matched standard solutions were linear in the range of 0.69-500 ng/g with a coefficient of determinations ≥0.9962. The method provided high extraction recoveries (70-99%) and enrichment factors (140-198), and an acceptable precision (relative standard deviations ≤7.1%).

Application of microcrystalline cellulose as an efficient and cheap sorbent for the extraction of metoprolol from plasma and wastewater before HPLC-MS/MS determination.

A dispersive solid-phase extraction method based on a new sorbent has been performed on plasma and wastewater samples to determine metoprolol by high-performance liquid chromatography-tandem mass spectrometry. In this study, the analyte was adsorbed from the samples onto microcrystalline cellulose as a green and efficient sorbent and then eluted for use in the determination step. In the mass spectrometer, the analyte was detected in the positive mode and selectivity of the analysis was increased by sequential mass analysis through multiple reaction monitoring. All of the effective parameters in the extraction of metoprolol from plasma and wastewater were optimized. Under optimal conditions the method was linear in the ranges of 1-1,000 and 0.1-1,000 ng/ml in plasma and wastewater samples, respectively. The detection limits of the method were 0.30 and 0.03 ng/ml in plasma and wastewater samples, respectively. The data showed that the method provides low detection limit, wide linear range, good precision and high extraction recovery. Finally several plasma and wastewater samples were successfully analyzed using the method. The use of a small amount of a green and inexpensive sorbent and a low volume of plasma without the need for further pretreatment steps are the main advantages of the method.

Development of dispersive solid-liquid extraction method based on organic polymers followed by deep eutectic solvents elution; application in extraction of some pesticides from milk samples prior to their determination by HPLC-MS/MS.

An effective extraction procedure based dispersive solid phase extraction was developed for the extraction of different pesticides (dimethoate, imidacloprid, pirimicarb, carbaryl, fenitrothion, hexythiazox, and phosalone) from milk samples. The analytes were determined by high performance liquid chromatography-tandem mass spectrometry. In this method, an organic polymer (polystyrene) was dissolved in a water-miscible organic solvent (tetrahydrofuran) and it was injected into the aqueous phase obtained from milk sample after deprotonation. By this action the sorbent (polymer) was precipitated and dispersed in the solution as tiny particles. By doing so, the pesticides were adsorbed onto the sorbent. After that, the sorbent was separated by centrifugation and the adsorbed analytes were eluted by tetrabutylammonium chloride: dichloroacetic acid deep eutectic solvent. After optimization, the method validation was followed according to Food and Drug Administration and International Research Council guidelines and the results showed that wide linear ranges (0.93-500 ng/mL) and low limits of detection (0.09-0.27 ng/mL) and quantification (0.31-0.93 ng/mL) were obtained. Extraction recoveries and extraction and enrichment factors were in the ranges of 81-94% and 162-188, respectively. Relative standard deviations were less than 9% for intra- (n = 6) and inter-day (n = 6) precisions at three concentration of 2, 5, and 25 ng mL-1 of each analyte. The developed method was successfully applied to twenty cow milk samples for determination of the pesticides.

Synthesis of polystyrene-polyricinoleic acid copolymer containing silver nano particles for dispersive solid phase microextraction of molybdenum in water and food samples.

Polystyrene-polyricinoleic acid copolymer containing silver nano particles (AgPSrici) was synthesized and used in separation of molybdenum from different aqueous and foodstuff samples during a dispersive-µ-solid phase extraction approach. The synthesized nano particles were verified using Fourier transform infraredspectroscopy. An electrothermal atomic absorption spectrometry has been used for measurement of the studied ions. AgPSrici amount pH, sample volume, elution solvent kind, and the time of extraction were the effective parameters that were optimized by one-variable-at-one-time method. Analytical data of the method was calculated and limit of detection, relative standard deviation, limit of quantification were 0.022 µg L-1, 2.9%, 150, and 0.066 µg L-1, respectively. The synthesized adsorption capacity was obtained 170 mg g-1.Accuracy of the method was studied by performing the method on certified reference materials and the presence of different interfering ions was studied. Molybdenum content of different water and foodstuffs was determined by the introduced method.

Air-Assisted Alkanol-Based Nanostructured Supramolecular Liquid-Liquid Microextraction for Extraction and Spectrophotometric Determination of Morin in Fruit and Beverage Samples.

A new air-assisted liquid-liquid microextraction method based on alkanol nanostructured supramolecular solvents coupled to spectrometric analysis was developed for extraction, preconcentration, and spectrophotometric determination of morin. Al(III)-morin complex was performed at pH 4.5. Four different alkanol-based SUPRAS (supramolecular solvents) were prepared for the separation and preconcentration of Al-morin complex from aqueous solution by using vortex and centrifugation. Effect of analytical variables and tolerance limit of matrix ions were investigated. Under the optimum conditions, detection limit, quantification limit, relative standard deviation, preconcentration factor, and enhancement factor were found as 3.5 µg L-1, 10 µg L-1, 3.1%, 120, and 95, respectively. The accuracy of the method was performed with standard addition. The obtained results demonstrated the applicability of the method for the separation, preconcentration, and determination of morin in fruit and beverage samples. The method also complies with green chemistry principles as it uses green solvents, reduces reagent volumes, and produces low amounts of waste. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s12161-021-02111-3.