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Review:
Magnetic Solid Phase Extraction for Determination of Dyes in Food and Water Samples Ruba Fahmi Abbas*.
Mohammed Jasim Mohammed Hassan, and Ahmed Mahdi Rheima Department of Chemistry.
College of Science.
Mustansiriyah University.
Baghdad 14022.
Iraq * Corresponding author:
email: rubaf1983@uomustansiriyah.
Received: January 3, 2023 Accepted: May 13, 2023 DOI: 10.
22146/ijc.
Abstract: Recently, magnetic solid-phase extraction (MSPE) is an important technology due to its use in analytical chemistry, biotechnology, and medicinal fields.
MSPE shows rapid isolation of target analyte from large volume samples, the huge surface area of magnetic nanoparticles (MNP.
, and simplicity in application due to using an external magnetic field instead of using packing column, centrifuge, and filter papers.
The aim of this review is to evaluate the extraction and determination of dyes in food and water samples by using the MSPE technique.
Keywords: adsorption.
magnetic solid phase extraction.
n INTRODUCTION There are more than a thousand different types of dye that can be commercially and frequently used in the textile, food, photography, cosmetics, plastics, and pharmaceutical industries.
Dyes are at the forefront of the pollutant due to being hard to remove from clean water .
Dyes have a complex chemical structure that makes them more resistant to fading on exposure to water, light, and chemical materials.
Because of that, many dyes are hard to remove or decolorize from wastewater.
so, dyes are an effective risk to water, soil, fauna, plant, cattle, and For example, the highest toxicity was found in the diazo direct and basic dyes .
Due to mentioned reasons, dyes should be determined in different environmental samples by using suitable extraction methods, such as the liquid-liquid extraction (LLE) from aqueous solutions followed by UVAevisible spectrophotometer for methylene blue dye .
, liquid-liquid microextraction (LLME) coupled with HPLC-DAD for Sudan dyes from tomato chili sauces .
, dispersive liquid-liquid microextraction (DLLME) based on the salting-out phenomenon followed by HPLC for Sudan dyes in turmeric powder, chili sauce, and water samples .
, solid-phase extraction (SPE) coupled with LC-ESI-MS/MS of disperse dyes in water samples .
, solid-phase microextraction (SPME) coupled with UPLCMS for Sudan dyes in tomato sauce and hot-pot samples Ruba Fahmi Abbas et al.
, microextraction by packed sorbent (MEPS) coupled with gas chromatography-mass spectrometry (GCAeMS) of azo dyes in textiles .
, matrix solid-phase dispersion (MSPD) followed by HPLCAeDAD of Sudan dyes in condiments and sauces .
, and stir-bar sorptive extraction (SBSE) coupled with HPLC of Sudan dyes in fruit juice and lake water samples .
Extraction methods require a long time, filter papers, centrifuge, slow packing of sorbent into the column, and a large volume of sample or solvent.
To overcome these limitations, magnetic solid-phase extraction (MSPE) offers a quick extraction method that has ease of preparation with large-scale production, ease of operation by applying an external magnetic, and ease of surface modification due to many hydroxyl (AeOH) groups on the surface of iron oxide.
Moreover, it is considered a green chemistry method because of the ease of recoverability of magnetic particles that can be reused after rinsing a few times.
It requires a small volume of sample and solvent without using filter papers and a centrifuge .
The aim of this review is to present the MSPE technique used for the extraction of dyes in food and water samples.
n CLASSIFICATION OF DYES There are many structural classifications of dyes, such as disperse, base, acidic, anthraquinone-based, diazo, azo, and metal complex dyes.
Dyes are classified Indones.
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in Table 1 according to their solubility in water, chemical constitution, and application in the industry .
while the chemical structure of some dyes examples are listed in Table 2.
Table 1.
Classification of dyes Type of dye Acid dyes .
nionic dye.
Solubility Soluble in water Direct dyes .
nionic dye.
Soluble in water when in the presence of salts and electrolytes Soluble in water with the sodium salt of sulphonic acid groups Soluble in water as chloride, sulfate, or nitrate salts Reactive dyes .
nionic dye.
Basic dyes .
ationic dye.
Functional group or constituent Sulphonic, carboxylic acid, azo, anthraquinones, triarylmethane, iminoacetone, nitro, nitrous, and/or Azo compounds with thiazoles, phthalocyanines, and oxazines Application Nylon, silk, modified acrylic, wool, paper, food, and Azo, anthraquinone, and phthalocyanine Fiber .
otton, wool, or nylo.
Azo, anthraquinone, triarylmethane, methane, thiazine, oxazine, acridine, and Modified acrylic, modified nylon, modified polyesters, and papers, and some of them have biological activity and are used in medicine as antiseptics Dyeing of nylon, polyamide, and polyester Dyeing cellulosic fibers, such as leuco-soluble salts, after reduction in an alkaline bath .
odium hydrosulfit.
Applied to cotton, linen, cotton, and jute after alkaline reduction bath, with sodium sulfite as reducing agent Dispersive dyes .
on-ionic dy.
Vat dyes .
on-ionic dy.
Insoluble in water Azo dyes Insoluble in water Anthraquinone and indigo Sulfurous dyes Insoluble in water but can be made soluble in water by treating them with reducing agents Soluble in water Contain sulfur linkage within their molecules Insoluble in water Acid Yellow 23 .
Acid Orange 7 .
Acid Red 92 .
Acid Violet 43 .
, 4hydroxypropylamino-3-nitrophenol .
itro anilin.
HC Yellow No.
itro anilin.
, pphenylenediamine, p-aminophenol, 4-amino2-hydroxytoluene .
romatic substitute.
Fluorescent dyes .
roup of the Dye precursors Ruba Fahmi Abbas et al.
Fluorescent carbonyl dyes .
oumarins, naphthalimides, perylenes, benzanthrone derivatives, benzoxanthones, and benzothioxanthone.
, rhodamines, and methine fluorescent dyes Cotton and regenerated cellulose, paper, leather, and Fluorescent dyes for textiles, daylight fluorescent pigments, dyes for lasers, solar collectors, electroluminescence, analytical, biological, and medical Commercial hair dying systems can be divided into two main categories, oxidative or nonoxidative Indones.
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Table 2.
Examples of dyes Type of dye
Acid dyes Functional group or Anthraquinone Molecular formula
Structure H3C
C32H28N2Na2O8S2
CH3
Ref.
CH3
CH3
ONa
ONa
H3C
CH3
Direct dyes Direct red 243 C38H28N10Na4O17S4 Reactive dyes Reactive blue 109 C25H12Cl2N9Na5O16S5 Basic dyes Methylene blue (Basic Blue .
C16H18ClN3S
Dispersive Dispersive red 60
C20H13NO4
Vat dyes Vat blue 5
C16H6Br4N2O2
Sulfurous dyes Sulphur blue 7
C13H14N2O
Fluorescent Disperse yellow 186
C21H19N3O
Ruba Fahmi Abbas et al.
Type of dye Dye Indones.
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Functional group or Acid yellow 23 Molecular formula Structure ONa C16H9N4Na3O9S2 NaO S Ref.
N N
NaO n CLASSIFICATION OF MAGNETIC MATERIALS There are four types of classification of magnetic materials depending on how they react with the magnetic field as described in Fig.
Ferromagnetic or superparamagnetic materials have been used widely in the MSPE technique as sorbent magnetic nanoparticle forms due to their high magnetic moments, ease of preparation, biocompatibility, and small size particles.
Chemical, biological, and physical methods have been used for synthesizing iron oxides like magnetite (Fe2O.
, spinel ferrites (MFe2O.
, and maghemite (-Fe3O.
n HISTORY AND PRINCIPLES OF MSPE The first authors to publish on MSPE were Safarik et al.
It depends on adding a magnetic sorbent into an aqueous sample to adsorb the target analyte.
Then, the sorbent target analyte is separated by using an external magnetic field.
After that, the addition of solvent to the analyte with used external magnetic again to collect the liquid analyte, which is determined by different analytical techniques .
The mechanism separation of MSPE is based on the interaction between the surface functional groups of the sorbent with the analyte.
The types of interactions are dispersion, ionic, hydrogen Fig 1.
Classification of magnetic materials Ruba Fahmi Abbas et al.
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bonding, dipole-induced dipole, and dipole-dipole forces.
The dipole-dipole interactions, hydrogen bonding, and AA interactions are the base of the analyte retention mechanism, but chemical bonding interactions are not used in the separation and retention of analyte because of their irreversibility.
Other properties affect the interaction of the sorbent with the analyte, such as solubility, concentration, and polarity of the analyte with the choice of the right sorbent and solvent .
MSPE principles include three steps: first, the analyte was captured or adsorbed by the addition of MNPs into the sample solution (MNPs are dispersing in the sample solutio.
Then, the separation step uses the external magnet to separate the target analyte from the The last is the desorption step, which is analyte desorption from the surface of MNPs using an appropriate solvent.
Acidic solutions are used as a good solvent for the inorganic analyte and an organic solvent is used for the organic analyte.
Then.
HPLC coupled to MS or UV-Vis is often preferred for the separation and determination of the analyte (Fig.
n PREPARATION OF MAGNETIC
NANOPARTICLES
The magnetite of Fe3O4 and -Fe2O3 are widely used in the preparation of the magnetic core for the MSPE method .
Many methods have been used for the preparation of Fe3O4, such as thermal decomposition, microemulsion, high-energy ball mill, hydrothermal synthesis, sonochemical synthesis, and co-precipitation.
The advantage of a thermal decomposition method to obtaining a narrow particle size distribution of MNPs, size control, and a high degree of crystalline.
This method is based on the decomposition of Fe.
3 with oleylamine, an 1,2-alkanediol and oleic acid in a high boiling point ether .
Microemulsion method based on microemulsion route above room temperature .
AC).
The microemulsion solution consists of forming the ternary system cyclohexane .
rganic phas.
/Brij-97 .
non-ionic surfactan.
/aqueous solution of FeSO4A7H2O/FeCl3A6H2O in the different mole ratio.
MNPs obtain from this method are higher in saturation magnetization and smaller in size .
A high-energy ball mill is a simple and low-cost technique.
Ball milling in a hardened steel vial was used for prepared the sample (Fe2 /Fe3 ), the molar ratio of Fe2 /Fe3 was 20:1, and the sample was milled to 96 h with a rotation speed of 200 rpm to obtain a 12 nm size of the magnetite particles .
In the hydrothermal synthesis method, the average diameters were 25 or 14 nm for -Fe2O3 or Fe3O4.
Hydrothermal reaction FeSO4 solution was heated at 473 K and using n-decanoic acid (CH3(CH.
9COOH) or n-decylamine (CH3(CH.
9NH.
as a surface modifier.
At a higher temperature over room Fig 2.
Steps of dye determination with MSPE Ruba Fahmi Abbas et al.
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temperature, the solubility of surface modifier increased in water, but the dielectric constant of water decreased and reacted with the surface of the nanoparticles.
This method is environmentally economical and without the use of organic solvents .
Sonochemical synthesis of Fe.
3 in water under an argon atmosphere with tetraglyme as a solvent.
Water amount had allowed control of the surface area and size of MNPs to obtain surface-modified ultra-small .
Ae2 n.
Coprecipitation is the simplest method used to prepare magnetite MNPs from aqueous FeCl2A4H2O/FeCl3A6H2O solutions with a concentration ratio of 2:1 by the addition of ammonia in a vacuum or nitrogen at 80 AC or less.
This method was used to obtain magnetite MNPs with diameters of 2Ae4 nm .
The morphology and microstructure of the MNPs were characterized by IR.
XRD.
TEM, and SEM.
n MODIFICATION OF MAGNETIC
NANOPARTICLES
Surface modification of MNP was used to ensure sensitivity and selectivity for the target analyte and to avoid weakened magnetism due to agglomerate and Surface modification with Fe3O4 MNPs is commonly used to functionalize the surface of the particles and improve their selectivity for specific Fe3O4 MNPs have similar properties to Fe2O3 MNPs or FeO MNPs, but they are typically more stable, high magnetization, high surface area, and large surfaceto-volume ratio.
Fe3O4 MNPs is that they have a higher surface area than FeO MNPs, which can improve their binding capacity for target analytes .
Fe3O4 has been intensively investigated for the modification of MNPs because of its superparamagnetic, non-toxic, low Curie temperature, high coactivity, and Physical modification methods include plasma radiation, ultraviolet, adsorption, and deposition of the surfaces.
In the chemical modification, the surface of MNPs was changed by chemical reactions.
The external layer of MNPs was modified by three main materials: inorganic substances, organic substances, and metal-organic frameworks (MOF.
(Fig.
n MODIFICATION OF INORGANIC
SUBSTANCES
One of the well-coated is SiO2, which is prepared by the sol-gel method.
This method's advantage is to obtain a spherical particle's shape, a size-controlled and it is considered a simple method for synthesizing MNPs .
Metallic oxides such as ZrO2.
CoFe2O4.
CoO.
NiO.
TiO2, and Al2O3 are usually used to modify MNPs.
Coating using metallic oxide provides several advantages, such as the prevention of agglomeration and increased stability biocompatibility, and hydrophilicity of MNPs.
For example.
Fe3O4@Al2O3 core-shell NPs were more air-stable than the naked Fe3O4 NPs.
Fe3O4@ZnO core-shell NPs were antioxidation and Fe3O4@CoFe2O4 have more magnetic properties than Fe3O4 NPs .
Composite materials were used in MSPE methods, such as Fe3O4@ZrO2@N-cetylpyridinium and Fig 3.
Materials used for modification of the MSPE method Ruba Fahmi Abbas et al.
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alumina-coated Fe3O4 MNP modified by dithizone and sodium dodecyl sulfate (SDS) in acidic media .
Ring-structured compounds and carbon-based have been adsorbed by graphene and carbon nanotubes from different samples.
For example.
Fe3O4@SiO2@G@PIL was magnetite graphene modified with ionic liquids and through electrostatic interactions.
graphene oxide was modified with the amino-functional silica-coated Fe3O4spheres .
n MODIFICATION OF ORGANIC SUBSTANCES There are many advantages of polymer It can effectively prevent MNPs oxidation, reduce agglomeration, and dipole-dipole interaction to become weakened between MNPs.
3D network polymer types with stability and adsorption capabilities are molecularly imprinted polymers (MIP.
Covalent organic frameworks (COF.
modification allows through van der Waals forces, hydrogen bonding, and the sizeexclusion effect to adsorb target analyte .
Nonpolymer materials include two types.
the first type is surfactants, which include octadecyl trimethyl ammonium chloride (OTAB), cetyltrimethylammonium bromide (CTAB), and SDS, which have a good extraction ability, high chemical stability, and large specific surface The second type of non-polymer material is small organic molecules, including oleic acid and fatty acid, which improve the stability and dispersion of MNPs .
n MODIFICATION OF METAL-ORGANIC FRAMEWORKS (MOF.
SUBSTANCES Metal-organic frameworks (MOF.
are crystalline inorganic-organic hybrid materials that give rise to new materials which have an internal surface area, porous, tunable pore size, and hollow structure.
Magnetic MOFs materials were used in MSPE, such as MOF-5 (Zn4O(BDC).
(BDC=1,4-benzenedicarboxylat.
with a cubic 3D porous structure.
ZIF-8([Zn(MeIM).
) and ZIF67 ([Co(MeIM).
) (MeIM=2-methylimidazol.
The advantages of MOFs are large pore volume, mechanical and chemical stability, superparamagnetism, and working at a high temperature, making MOFs more useful for the MSPE .
Overall, the choice of inorganic, organic.
Ruba Fahmi Abbas et al.
or MOF modification will depend on the specific application and the properties required for the MNPs.
Organic modifications are often preferred for biological applications, where biocompatibility and dispersibility in solution are critical, while inorganic modifications are often preferred for chemical and environmental applications, where chemical stability and magnetic properties are more important.
MOF-coating MNPs can provide higher stability and selectivity, and they can be used in a variety of applications, including water treatment, drug delivery, catalysis, lithium-ion batteries, and luminescence .
n MAGNETIC TEXTILE SOLID-PHASE
EXTRACTION (MTSPE)
MTSPE is using magnetically modified textile materials as a new type of pre-concentration method.
Includes a piece of fabric textile 1 y 1 cm2 with an office stapler, which is rapidly and easily separated magnetically by using an external magnetic field .
MTSPE is considered a green chemistry method due to its advantage of simplicity, readily, and low cost.
Furthermore, this method is easy separation and recovery of the analytes, reducing the need for additional purification steps.
Many materials were used for modified the textile fibers to provide a high surface area and a porous structure as a 1% chitosan solution was applied to determine azorubine, indigo carmine, tartrazine, and blue fountain ink dyes .
Polysaccharide -carrageenan combination with agarose was applied to determine Nile blue A, safranin O, and methylene blue .
n APPLICATIONS AND OPTIMIZATION OF THE MSPE MNPs are widely used in analytical chemistry, medicine, bioanalytical, environmental pollutants, and food samples.
MSPE has been used to determine estrogens in milk .
, phthalic acid esters in carbonated soft drink .
, tetracyclines in milk .
, organophosphorus pesticides in water .
, phthalate monoesters in urine .
Co(II) and Hg(II) in water and food .
, polycyclic aromatic hydrocarbons in grilled meat .
, lignans in sesame oil .
, a free fatty acid in edible oils .
, and Indones.
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non-steroidal anti-inflammatory drugs .
aproxen, ketoprofen, and diclofena.
in biological and water and samples .
However, the large surface area and high magnetic responsiveness of magnetic nanoparticles make them excellent sorbents for a variety of applications.
achieve the best extraction efficiency, various conditions, such as the sorbent categories, the pH, sorbent amount, extraction time, desorption solvent, the volume of desorption solvent, desorption temperature, and desorption time, were optimized (Table .
Table 3.
Optimization factors of the MSPE procedure Vol.
Desorption Desorption Ref.
Methanol 2 mL 0 min .
2 mL .
Methanol containing 1% acetic acid Acetonitrile 0 min .
0 mg 15 min Ethanol 2 mL 0 mg 108 min 0 mg 20 min Fe3O4NH2@MIL-101 0 mg cMWCNT-Fe2O3 Fe3O4-fullereneactivated carbon Sample Sorbent Extraction mg/mL 20 min Acetone with 5% acetic acid 0 mg 15 min 0 mg 10 min MG(Cationi.
MWCNT@Fe3O4 6Ae8 0 mg Sudan I.
II, i and IV.
zo dy.
Fe3O4@PANI Fe3O4NH2@HKUST1@PDES MPCDPs(C) Analyte Magnetic Basic violet 7.
Basic M-S-RGO red 13 and Basic CV.
MV.
MB, and MNPs-POLP MR and MO MHNTs Desorption 0 min .
1 mL Room
Room
65 AC
Methanol 3 mL .
2 min Ethyl acetate 2 mL 0 min .
0 mg 15 min Acetonitrile 3 mL 0 min .
01 mg 15 min 500 L 0 min .
Triphenylmethane -Fe2O3@CNM dyes (MG and CV) 0 mg 5 min 1 mL Room Sudan I.
II, i and MG and CV magnetic Fe3O4 NPs Fe3O4@SiO2-Flu 20 min Methanol NaOH 10Oe3 M Methanol 2% formic Methanol 5 mL 0 min .
0 mg 20 min Methanol 5 mL 0 min .
Rhodamine B Sudan red Sudan dyes (I.
II, i, and IV) Fe3O4@SiO2@IL 3
Fe@NiAl-LDHs 7
Fe3O4 MNPs/PSt 4
0 mg
0 mg
10 min 60 min 15 min Ethanol
Acetone Acetonitrile 0 mL 5 mL 0 mL Room
Room
30 AC
Room 0 min 0 min 5 min .
Sudan I.
II, i and Sudan I-IV.
Para Red and Sudan Red Sudan Black B.
Sudan Red 7B.
Para Red and Sudan I.
II, i.
IV Sunset yellow, allure red and Ruba Fahmi Abbas et al.
1 mL Room
25 AC
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Analyte Sudan dyes (I.
II, i, and IV) Congo Red and Basic Red 2 Rose Bengal Acridine orange.
Amido black 10B.
Bismarck brown.
Congo red.
Crystal violet.
Malachite green.
Safranin O Acridine orange.
CV.
MG.
Safranin O.
Methylene blue MG and CV n Magnetic Sorbent Extraction 0 mg 10 min Methanol 0 mg 15 min C-MIONPs Magnetically modified Spent coffee grounds 0 mg 90 min Methanol and Methanol Methanol 0 mL 0 mL Magnetically modified S.
horneri biomass Fe3O4/GO 13 mg 15 min Acetonitrile/ace 0.
2 mL tic acid
Magnetic argan
press cake
(MNC)
ZIF-8@CoFe2O4 FOOD ANALYSIS Azo dyes are used for coloring food products due to their low cost and high stability to the oxygen, pH, and light compared to the dyes obtained from natural sources .
Many countries have forbidden synthetic azo dyes using in food products because they are shown to be genotoxic, potentially neurotoxic, and carcinogenic additives .
For example.
Tartazin dye causes genotoxicity in rodents, and allura red and brilliant blue cause allergic reactions.
Tartrazine, sunset yellow, erythrosine, and allura red can be carcinogenic .
MSPE was successfully used for the removal, analysis, and determination of cationic dyes from different samples .
ood and wate.
(Table .
Cui et al.
developed a novel adsorbent magnetic sulfonated reduced graphene oxide (M-S-RGO) based on (M-S-RGO) with HPLCAeMS/MS for analysis and determination of Basic violet7.
Basic red 13 and Basic orange 21 in food samples.
This method was applied for a wide range of basic dyes with lower LOD 01Ae0.
2 g/L .
A new Fe3O4-NH2@HKUST-1@PDESMSPE (Polymeric deep eutectic solvents (PDES)) based on 3-acrylamidopropyl trimethylammonium chloride/Dsorbitol functionalized amino-magnetic (Fe3O4-NH.
metal-organic framework (HKUST-1-MOF) composite.
Ruba Fahmi Abbas et al.
Desorption Vol.
Desorption 0 mL Room Sample Desorption Ref.
0 min .
0 min .
0 min .
Room 0 min .
Room
25 AC
Room was used for the extraction and determination of MG and CV cationic dyes from fish samples, with the successful recovery of 89.
43Ae100.
65% for MG and 95.
29Ae98.
for CV indicating that this method was a successful application in extracting cationic dyes in fish samples .
Sudan dyes are class 3 carcinogens, so using these dyes in food is considered illegal.
Determination Sudan dyes were developed by using magnetically modified porous -cyclodextrin polymers (MPCDP.
coupled with HPLC.
MPCDPS was a good analytical adsorbent for the separation and concentration of Sudan dyes in food and water samples .
Magnetic trimeric chromium octahedral metal-organic framework (Fe3O4NH2@MIL-.
combined with HPLC was used to determine Sudan I-IV.
Para Red, and Sudan Red 7B in tomato sauce with a good RSD of O 9.
2% .
Sudan Black B.
Sudan Red 7B.
Para Red, and Sudan I.
II, i.
IV were extracted by using Fe2O3 magnetic nanoparticle functionalized with carboxylated multiwalled carbon nanotube .
MWCNT--Fe2O.
coupled with HPLC in chili products and ketchup .
Fe3O4 MNPs were used for the extraction of Sudan dyes from chili oil, chili powder, tomato paste, and different water samples coupled with HPLC for separation and determination of Indones.
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Table 4.
Application of MSPE Analyte Type of dye Magnetic material Sample Technique Limit of 01Ae0.
2 g/L 70Ae110% .
MR:85Ae87% MO: 89Ae93% 0Ae92.
4Ae106.
MG: 89.
43Ae CV: 95.
29Ae Food samples:
8Ae102.
Water samples:
3Ae103.
6Ae92.
Recovery Ref.
Illegal basic dyes (Basic violet 7.
Basic red 13 and Basic orange .
MV.
MB.
MG.
CV, and NR from MR and MO Cationic M-S-RGO Cationic MNPs-POLP Frozen grass carp, frozen yellow croaker, and tomato Aqueous solution Anionic azo dye MHNTs Water samples MG and GV Cationic HPLC-FLD Sudan I.
II, i and MG and CV Azo dye MSPE method based on Water samples MWCNT@Fe3O4NPs Water samples Fe3O4@PANI Cationic Fe3O4-NH2@HKUST1@PDES-MSPE Fish samples UV-Vis Sudan I.
II, i and Azo dye MPCDPs(C) and MPCDPs(M) Food samples and water samples HPLC Sudan I-IV.
Para Red and Sudan Red Sudan Black B.
Sudan Red 7B.
Para Red and Sudan I.
II, i.
IV Sunset yellow, allure red and tartrazine Triphenylmethane dyes (MG and CV) Azo dye Fe3O4-NH2@MIL-101 Tomato sauce HPLC-DAD MR: 0.
042 g/L MO: 0.
050 g/L MG: 0.
22 ng/mL GV: 0.
09 ng/mL 041Ae0.
ng/mL MG: 98.
ng/mL CV: 23.
ng/mL MPCDPs(C):
013Ae0.
ng/mL MPCDPs(M):
028Ae0.
ng/mL 5 mg/kg Azo dye cMWCNT--Fe2O3 Chilli products and HPLC 84 ng/mL .
Anionic azo dye Fe3O4-fullereneactivated carbon -Fe2O3@CNM-based MSPE Water samples Capillary LC-MS/MS 0 mg/L 95Ae106% .
004 ng/mL .
HPLC 02 g/L MG: 73.
4Ae CV: 83.
1Ae Water samples:
9Ae98.
Food samples:
9Ae109.
UV-Vis
HPLC
HPLC
UFLC-UV
82Ae3.
27 ng/L 08 g/L 002Ae0.
005 g/L 0039, 0.
0057, and 017 ng/mL 05Ae0.
07 g/L 88Ae96% 0Ae100.
6Ae105.
3Ae96.
4Ae109.
Cationic Sudan I.
II, i and Azo dye Magnetic Fe3O4 NPs MG and CV Rhodamine B Sudan red Sudan dyes (I.
II, i, and IV) Cationic Cationic Cationic Azo dye Fe3O4@SiO2-Flu Fe3O4@SiO2@IL Fe@NiAl-LDHs Fe3O4 MNPs/PSt Sudan dyes (I.
II, i.
Azo dye and IV) Congo Red and Basic Red 2 Rose Bengal Congo red is azo dye and Basic Red 2 is Xanthenes dye Ruba Fahmi Abbas et al.
Magnetic argan press cake nanocellulose (MNC) ZIF-8@CoFe2O4 C-MIONPs Spring water, lake water, fishpond water, seawater, and mineral wastewater Food samples .
hili oil, chili powder and tomato past.
and water samples .
ap and river wate.
Water samples Chili powder
Water samples Red wines, juices, and mature vinegar
HPLC-MS/MS
UV-Vis
HPLC
UFLC-UV
Barbeque and ketchup sauces Capillary liquid Aqueous solution UV-Vis Brucella Antigen solution and water samples from the Karoon River UV-Vis 91 y 10Oe3 g/mL 7Ae98.
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Limit of Analyte Type of dye Magnetic material Sample Acridine orange.
Amido black 10B.
Bismarck brown.
Congo red.
Crystal violet.
Malachite green.
Safranin O Acridine orange.
CV.
MG.
Safranin O.
Methylene blue MG and CV Acridine orange is a fluorescent dye.
Black 10B.
Congo red.
CV, and MG are azo dyes.
Safranin O is azonium Acridine orange isa fluorescent dye Magnetically modified Spent coffee grounds Aqueous Solution UV-Vis Magnetically modified horneri biomass Aqueous solution UV-Vis Cationic Fe3O4/GO magnetic Water samples HPLC MG: 0.
091 g/L CV: 0.
120 g/L 5Ae116.
dyes, with LOD values down to 0.
02 g/L for all samples .
Fe3O4@SiO2NPs were coated with three ionic liquids [HMIM]PF6, [BMIM]PF6, and [OMIM]PF6 to prepare fluconazoleAcfunctionalized Fe3O4@SiO2 nanoparticles (Fe3O4@SiO2@IL) coupled with HPLC for the determination of Rhodamine B in Chili powder.
RSD value was 0.
51%, and this MNPs could be reused up to 10 times .
Nanocomposite of polystyrene-coated magnetic nanoparticles (MNPs/PS.
coupled with UFLC-UV was used for the determination of Sudan dyes in different types of drinks and RSDs were lower than 9.
6% .
Sudan dyes in the barbeque and ketchup sauces were extracted using magnetic/non-magnetic argan press cake nanocellulose coupled with capillary liquid chromatography and SD achieved was lower than 3.
46% .
n WATER ANALYSIS Synthetic dyes are used to produce plastics, rubber and textiles which cause environmental pollution .
ater and soi.
Most dyes are toxic and cause skin irritation, dermatitis, and allergy.
They are harmful to humans and aquatic biota.
MSPE is a new technique that has been used in the extraction of dyes from wastewater, tap water, and river water samples.
MSPE was used for the extraction of dyes from water samples due to their selectivity, low volume of solvents, and high throughput (Table .
Adsorption of cationic dyes .
ethyl violet (MV), methylene blue (MB), malachite green (MG), crystal violet (CV), and neutral red (NR)) from aqueous solution by using Platanus orientalis leaf powder (MNPs-POLP) coupled with UV-Vis spectrophotometer .
Mixed hemi micelle based on magnetic halloysite nanotubes and ionic liquids (MHMSPE) was prepared from ionic liquid Ruba Fahmi Abbas et al.
Technique Recovery Ref.
[C16mimB.
and MHNTs to determination of anionic dyes .
ethyl red (MR) and methyl orange (MO)) in different water samples, lower RSD was achieved in this method, 2.
5Ae5.
4% for lake water, and 1.
6Ae3.
1% for tap water .
Multiwalled carbon nanotubes modifiedFe3O4 nanoparticles (MWCNT@Fe3O4 NP.
was used for extraction of MG and gentian violet (GV) dyes in water samples and followed by HPLC-FLD to give RSD values of 4.
6Ae5.
9% .
Sudan dyes were extracted by using Fe3O4@polyaniline particles (Fe3O4@PANI) coupled with UFLC-UV in water samples .
ake water, rainwater, surface water, reservoir water and tap wate.
and RSD were found in the range of 1.
6Ae6.
8% .
Fe3O4-fullerene-activated carbon followed by capillary electrophoresis was used for extraction and analysis of anionic dyes .
llure red, sunset yellow, and tartrazin.
in water samples and RSD was found to be less than 10% .
Caramelized carbonaceous shell-coated -Fe2O3 (-Fe2O3@CNM-based MSPE) coupled with LC-MS/MS was used for the extraction and analysis of MG and CV dyes in spring water, fishpond, lake, sea, and industrial wastewater.
RSD below 5.
2% for MG and RSD below 5% for CV dyes .
Cationic dyes (MG and CV) were extracted and determined using Fe3O4@SiO2-Flu followed by UV-Vis spectrophotometer in Caspian seawater and wastewater, and RSD was computed to be 4.
77Ae4.
Fe@NiAl-LDHs .
ayered double hydroxid.
coupled with HPLC was used for the extraction and determination of Sudan red dyes in Ming Tombs Reservoir water.
Changping Park water, and Binhe Park water, with low LOD from 0.
002 to 0.
005 g/L .
Adsorption of Congo Red and Basic Red 2 was achieved using coreAeshell heterostructure of 24 CoFe2O4-Zeolitic Indones.
Chem.
, 2023, 23 .
, 1181 - 1198
Imidazolate Framework-8 (ZIF-8@CoFe2O.
followed by a UV-Visible spectrometer with a high removal efficiency of 97% .
CTAB-coated magnetic iron oxide nanoparticles (C-MIONP.
coupled with a UV-Visible spectrometer were used for the separation and determination of RB dyes in Karoon river water and Brucella Antigen solution.
RSD values were found to be 1 and 1.
1% .
Adsorption of seven different types of dyes (Acridine orange.
Amido black 10B.
Bismarck brown.
CR.
CV.
MG.
Safranin O) was achieved by using a magnetically modified spent coffee grounds coupled with UV-Vis spectrometer in potable water .
Adsorption of acridine orange.
CV.
MG.
Safranin O, and MB by using low-cost adsorbent magnetically modified S.
biomass followed by UV-Vis spectrometer .
Finally.
Fe3O4/graphene oxide nanoparticles (Fe3O4/GO) coupled with HPLC were successfully applied to the extraction and determination of MG and CV dyes in the pond, lake, and river samples .
n CONCLUSION MSPE technique has the advantages of a simple synthesis of MNPs, selectivity to the target analyte, low cost due to using an external magnet which avoids the need for filtration or centrifugation steps, and avoiding using columns packed by sorbents that need to consume a long time to prepare these columns.
Moreover, its ability to extract and pre-concentrate target analytes from complex matrices such as food and water samples.
Dyes are often used in the food industry to enhance the appearance of food products.
MSPE can be used to extract and quantify these compounds in food and water samples due to its high selectivity, sensitivity, and simplicity of MSPE technique has been coupled with different analytical instruments such as UV-visible spectrometer.
HPLC.
LC-MS/MS, and capillary electrophoresis for the determination of dyes amount in food and water samples.
Most past studies focus on the determination of dyes in the food or water samples, so efforts should be made to expand studies to soils, sediments, and other environmental samples.
Future methods should seek to automate the MSPE method and couple it with the online system.
Ruba Fahmi Abbas et al.
n REFERENCES