Deep eutectic solvents (DESs) have recently attracted attention as a promising green alternative to conventional hazardous solvents by virtue of their simple preparation, low cost, and biodegradability. Even though the application of DESs in analytical chemistry is still in its early stages, the number of publications on this topic is growing. Analytical procedures applying dispersive liquid–liquid microextraction based on the solidification of floating organic droplets (DLLME-SFOD) are among the more appealing approaches where DESs have been found to be applicable.
Analysis Method | Analytes | Matrix (Amount) | Extractant (Volume) | Disperser DES (Molar Ratio) (Volume) |
Assistant Techniques | EF | LOD (µg/L) | % RSD | Ref |
---|---|---|---|---|---|---|---|---|---|
HPLC-PDA | Steroids (Triamcinolone acetonide, dexamethasone, testosterone, prednisolone, Cortisone, 1,4-androstadiene-3,17-dione, hydrocortisone acetate, Finasteride, 4-androstane-3,17-dione) |
Water (5 mL) |
1-Dodecanol (50 μL) | TBABr: acetic acid (1:2), (231 μL) | - | 44–112 | 1.0–9.7 | <5 | [31] |
HPLC-PDA | Preservatives (benzoic acid, sorbic acid, Methyl paraben, Ethyl paraben, Propyl paraben, Butyl paraben) |
Beverages (4 mL) |
1-Decanol (80 µL) |
TBABr: acetic acid (1:2) (200 µL) | Vortex (3 min) |
81–99 | 20–50 | <5 | [33] |
HPLC-UV | Pesticides (fipronil, fipronil-sulfide, fipronil-sulfone, boscalid) |
Water and wine (5 mL) |
1-Dodecanol (100 μL) |
Lactic acid: glucose: water (5:1:3), (2 mL) |
Vigorous shaking (1 min) |
NA | 0.8–1.3 | <15 | [35] |
GFAAS | Ni (II) and Co (II) | Water and food (10 mL) |
1-Dodecanol (75 μL) |
TBABr: acetic acid (1:2), (250 μL) | Ultrasonication (1 min) |
100 | 0.2 and 0.4 | <3.5 | [34] |
Analysis Method | Analytes | Matrix (Amount) | Extractant (Molar Ratio), (Volume) |
Disperser (Volume) |
Auxiliary Equipment | EF | LOD (µg/L) | % RSD | Ref |
---|---|---|---|---|---|---|---|---|---|
HPLC-VWD | Benzoylureas (triflumuron, hexaflumuron, flufenoxuron, lufenuron) |
Water (8 mL) |
[N8,8,8,1]Cl: 1-dodecanol (1:1), (50 μL) |
FeCl3 ethanol solution (250 μL) |
- | 91–97 | 0.11–0.35 | <5 | [38] |
HPLC-VWD | Benzoylureas (triflumuron, hexaflumuron, flufenoxuron, lufenuron, diflubenzuron) |
Water (8 mL) |
[OMIM]Cl: 1-dodecanol (1:2), (40 μL) | Vortex (3 min) |
- | 171–188 | 0.09–0.16 | <6 | [39] |
GC-MS | Aromatic amines (aniline, p-toluidine, p-chloroaniline, p-anisidine, 4-tert–butyl aniline) |
Water (10 mL) |
ChCl: n-butyric acid (1:2), (65 μL) |
Aspiration/dispersion (4 cycles) |
- | 790–940 | 0.0018–0.006 | ≤5.3 | [42] |
HPLC-FLD | PAHs (naphthalene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene) |
Water (20 mL) |
TBABr: decanoic acid (1:2), (80 µL) | NA | Ultrasonic bath (1 min at 35 °C) | 163–198 | 0.0007–0.0066 | <11 | [41] |
HPLC-UV | NSAIDs (ketoprofen, diclofenac) |
Human urine (8 mL) |
Menthol with the studied NSAIDs | NA | Water bath (50 °C) | 27–31 | 15–44 | <5 | [46] |
HPLC-UV | Antibiotics (amoxicillin, ceftriaxone) |
Hospital Sewage (10 mL) |
[DMIM]Cl: n-butanoic acid (1:2), (60 μL) | Vortex (5 min) |
Water bath (55 °C) | 164–172 | 0.005–0.100 | <5.2 | [43] |
UPLC-MS/MS | NSAIDs (diclofenac, flurbiprofen, ketoprofen, mefenamic acid) |
Bovine milk (5 mL) |
Menthol with the studied NSAIDs | Vortex (1 min) |
Heating to 50 °C | 81–102 | 0.01–0.03 µg/kg | <7 | [65] |
GC-MS | Pesticides (prometryn, diazinon, fenvalerate, fenamiphos–sulfone, fenpropathrin, bifenthrin, terbutryn, bromopropylate, deltamethrin, phosalone) |
Urine and plasma (5 mL) |
Menthol: phenylacetic acid (3:1), (41 μL) | N2 stream flow (2.0 mL/min for 2.5 min) | - | Urine (379–485) Plasma (158–194) |
Urine (0.002–0.017) Plasma (0.004–0.036) |
NA | [54] |
GC-MS | Pesticides (diazinon; prometryn; terbutryn; bifenthrin; fenpropathrin; bromopropylate; fenamiphos-sulfone; phosalone; fenvalerate, deltamethrin) |
Breath condensate and saliva (5 mL) |
Menthol: phenylacetic acid (3:1), (41 μL) | Air stream (FR = 2.0 mL/min, for 2.0 min) |
- | 79–97 | 0.002–0.059 | <7 | [55] |
GC-MS | Antidepressants (Amitriptyline, nortriptyline, Clomipramine, imipramine) |
Urine (5 mL) |
Menthol: decanoic acid (1:2), (54 μL) | 30% Na2SO4 (1 mL) |
NA | 122–147 | 0.013–0.025 | <11 | [52] |
GC-MS | OPFRs (Triphenyl phosphate, tripropyl phosphate, TCP, TBP, TCEP, TCPP, TEHP) |
Water (5 mL) |
BTPPB: 1-undecanol (1:4), (90 μL) |
Aspiration/dispersion (11 times) |
NA | 119–312 | 0.002–0.023 | <8.7 | [16] |
HPLC-UV | Curcuminoids (bisdemethoxycurcumin, demethoxycurcumin, curcumin) |
Curcumae Longae Rhizoma and turmeric tea (0.5 g) | TBACl: decanoic acid (1:1), (70 μL) |
Magnetic stirring at 40 °C | NA | 608–848 | 0.07–0.09 | <4.2 | [40] |
HPLC-UV | Aromatic amines (2-chloroaniline, 4-chloroaniline, 1-naphthylamine) |
Water (15 mL) | [P14,6,6,6]Cl: decanol (1:2), (40 µL) |
Ultrasound (60 s) | NA | 116–121 | 0.07–0.11 | <6.2 | [47] |
UPLC-MS/MS | Bisphenols (bisphenol S, bisphenol A, bisphenol B) |
Canned fruit (0.5 g) |
Menthol: undecanol (1:2), (300 μL) |
Acetonitrile (400 μL) | Vigorous shaking (2 min) | 4.4–4.9 | 0.0015–0.003 µg/g | <4.6 | [56] |
GC–FID | Pesticides (carbaryl, hexythiazox, pretilachlor, iprodione, famoxadone, sethoxydim, fenazaquin) |
Milk (5 mL) | ChCl: decanoic acid (1:2), (63 μL) |
Vortex (1 min) | Ultrasonic bath (7 min at 50 °C) | 320–445 | 0.90–3.9 | <7 | [44] |
HPLC-PDA | Strobilurin fungicides (Picoxystrobin, pyraclostrobin, trifloxystrobin) |
Water, juice, wine, vinegar (10 mL) | Thymol: octanoic acid (1:5), (120 μL) | Effervescence tablet [Na2CO3 (10 mg), citric acid (80 mg)] | NA | NA | 0.15–0.38 | NA | [57] |
HPLC-PDA | Benzophenone and UV filters (BP, BP-1, BP-3, PS, BS) |
Water (5 mL) | Decanoic acid: dodecanoic acid (2:1) (65 μL) | Aspiration/dispersion (6 cycles) |
NA | 41–50 | 0.045–0.54 | ≤4.2 | [66] |
HPLC-PDA | EDCs (BPA, BP, EE, DEST, 4-NP) |
Water (5 mL) | Nonanoic acid: decanoic acid: dodecanoic acid (1:1:1), (200 µL) |
Aspiration/dispersion (6 cycles) |
- | 38–134 | 0.96–2.3 | <7 | [67] |
HPLC-UV | Fungicides (azoxystrobin, fludioxonil, epoxiconazole, cyprodinil, prochloraz) |
Fruit juices and tea drinks (5 mL) |
Menthol: decanoic acid (1:1), (70 μL) | NA | Ultrasonication (9 min) | NA | 0.75–8.45 | <14.8 | [68] |
UV–Vis | Patulin | Fruit juice and dried fruit (2 mL) |
L-proline: glycerol (3:1), (410 μL) |
Aspiration/dispersion (6 cycles) |
NA | 150 | 3.5 | <5.6 | [58] |
HPLC-UV | Phthalic acid esters (DPP, BPP, DBP, DCHP, DEHP, DINP, DIDP, diisopentyl phthalate, di-n-pentyl phthalate) |
Teas Infusion (15 mL) and soft drinks (20 mL) | Menthol: acetic acid (1:1), (100 µL) |
NA | Manual vigorous shaking (1 min) | 3–12 | NA | 1–22 | [59] |
GC-MS | EDCs (DEP, DBP, DEHP, BPA, DEHA) |
Polyethylene packed injection solutions (5 mL) | Menthol: decanoic acid (1:2), (65 μL) | Aspiration/dispersion (4 cycles) |
NA | 395–470 | 0.014–0.033 | <7 | [69] |
HPLC-FLD | Endocrine disrupting compounds (estradiol, estriol, BPA, BPF) | Sewage | Octanoic acid: 1-dodecanol (1:3), (80 μL) | Vortex (1 min) | NA | 96–111 | 0.00133–0.00292 | <6.2 | [60] |
HPLC-PDA | Pyrethroids (bifenthrin, β-cypermethrin, deltamethrin) |
Corn, wheat, barley, oats Cereals (1 g) | Thymol: octanoic acid (1:4), (60 μL) | Acetonitrile (1.5 mL) | NA | NA | 2–2.7 μg/kg | <3.6 | [61] |
HPLC-UV | Bisphenols and PAHs (BPF, BPA, BPB, naphthalene, biphenyl, fluorene, phenanthrene, anthracene) |
Tea infusions (5 mL) |
Menthol: dodecanoic acid (3:1), (100 μL) |
Aspiration/ dispersion (9 cycles) |
NA | 15–18 | 0.16–0.75 | ≤2.3 | [62] |
HPLC-PDA | Benzoic acid and sorbic acid | Ketchup and powder bags of instant noodles (10 mL) | Menthol: p-aminophenol (1:2), (800 μL) | Vortex (2.6 min) |
NA | NA | 30 and 80 | <5.6 | [70] |
GC-FID | Pyrethroid insecticides (deltamethrin, cypermethrin, bifenthrin, cyhalothrin, permethrin) | Milk (10 mL) | Menthol: p-aminophenol (1:2), (94 μL) | Ammonia solution (300 μL) |
NA | 257–299 | 1.1–2.4 | ≤6.4 | [64] |
HPLC-UV | Anthraquinones (rhein, emodin, chrysophanol, physcion) |
Fried Cassiae semen tea infusions (10 mL) |
ChCl: octanoic acid (1:2), (100 μL) |
CO2 (H2SO4 and Na2CO3 reaction) |
NA | 94–104 | 80–110 | <3.3 | [71] |
HPLC-UV | Benzophenone-UV filters (BP-1, BP-2, BP-3, BP-6) |
Water (10 mL) | [P4,4,4,12]BF4: decanoic acid (1:9.4) |
CO2 | NA | 34–42 | 0.60–1.50 | <8 | [63] |
Analysis Method | Analytes (Details) | Matrix (Amount) | Extractant (Molar Ratio), (Volume, μL) |
Disperser | Assistant Techniques | Chelating Agent (Volume, μL) |
EF | LOD (µg/L) | % RSD | Ref |
---|---|---|---|---|---|---|---|---|---|---|
ETAAS | As, Se, Hg (Speciation) |
Child blood (10 mL) |
ChCl: Decanoic acid (1:2), (60 μL) | Vortex (5 min) | NA | DDTP (15 μL) | 98–106 | 0.015–0.10 | ≤5.8 | [75] |
GFAAS | Se (Speciation) |
Child blood (5 mL) |
ChCl: Decanoic acid (1:2), (60 μL) | Vortex (4 min) |
NA | DDTP (15 μL) | 112 | 0.05–5 | <3.5 | [76] |
UV-Visible | Se (Speciation) |
Water (5 mL) | BTPPB: 1-undecanol (1:4), (700 μL) |
Aspiration/ dispersion (7 cycles) |
NA | DAB (0.09 %) | 315 | 0.76 | ≤8.3 | [77] |
ETAAS | Cr (VI) | Urine (10 mL) |
BTPPB: phenol (128 μL) |
Sonication (1 min) |
NA | DPC | 34 | 0.002 | ≤4.7 | [79] |
GFAAS | Pb, Cd, Hg | Soil and vegetables (1 g) | [DMIM]: 1-undecanol (1:2), (50.0 μL) |
Vortex (4 min) |
Water bath (at 55 °C) | DDTP (15 μL) |
114–172 | 0.01–0.03 μg/kg | ≤7 | [73] |
GFAAS | Pb, Cd, Cu, As, Hg | Tea (0.5 g) |
[DMIM]: n-butanoic acid (1:2), (60 μL) | Vortex (4 min) |
Water bath (at 50 °C) | DDTP (20 μL) |
164–235 | 0.005–0.10 μg/kg |
≤3.5 | [72] |
GFAAS | Ni, Co | Food and Water (50 mL) | Menthol: decanoic acid (150 μL) | NA | NA | Br-PADAP (150 μL) |
50 | 0.3–0.4 | ≤3 | [53] |
GFAAS | Cd, Zn | Water and fruit juice (5 mL) |
Menthol: Sorbitol: Mandelic acid (1:2:1), (125 μL) |
Aspiration/dispersion (9 cycles) |
NA | DES | 23.4–24.8 | 0.12–0.15 | ≤4.2 | [78] |
GFAAS | Cd, Cu, Pb | Milk (5 mL) | Menthol: Sorbitol: Mandelic acid (1:2:1), (100 μL) |
Methanol (1.5 mL) | NA | DES | NA | 38–0.42 | ≤4.5 | [17] |
Analysis Method | Analytes | Sample Preatment | Matrix (Amount) | Extractant (Molar Ratio), (Volume) |
Disperser (Volume) |
EF | LOD (µg/L) | % RSD | Ref |
---|---|---|---|---|---|---|---|---|---|
IMS | Antibiotic residues (oxytetracycline, penicillin G, tilmicosin) | HLLE | Sausage (20 g) | PChCl: dichloroacetic acid: dodecanoic acid (1:1:1), (70 µL) |
Acetonitrile (2 mL) | 1260–1580 | 0.00152–0.00273 µg/g | <8 | [48] |
IMS | Antibiotic residues (oxytetracycline, penicillin G, tilmicosin) | CCSHLLE | Hamburger and cow liver (10 g) |
ChCl: pivalic acid (1:2), (75 μL) |
Acetonitrile (1 mL) | 670–900 | 0.0017–0.0028 | ≤6.2 | [50] |
GC/MS | Phytosterols (brassicasterol, campesterol, stigmasterol, β-sitosterol, lupeol) |
d-SPE | Edible oil (5 mL) |
ChCl: n-butyric acid (0.065 g: 80 µL, in situ formation) | Water bath (5 min at 75 °C) | 312–375 | 0.52–1.6 | ≤8.2 | [45] |
GC-MS | Pesticides (Dalapon, 2-methyl-4-chlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, fenoxaprop, haloxyfop) |
SBSE | Tomato juice (50 mL) | ChCl: n-butyric acid (1:2), (58 μL) |
NA | 2530–2999 | 0.007–0.014 | ≤12 | [49] |
GC-NPD | Organophosphorous pesticides (Etrimfos, fenthion, di-azinon, chloropyrifos) |
d-SPE | Edible oil (2.5 mL) |
ChCl: 3,3-dimethylbutyric acid (1:1), (15 µL) | NA | 170–192 | 0.06–0.24 | ≤9.2 | [51] |
This entry is adapted from the peer-reviewed paper 10.3390/molecules26237406