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. 2022 Jan 13;9:785830. doi: 10.3389/fchem.2021.785830

TABLE 2.

Applications of the microextraction techniques discussed in this review for determination of pharmaceuticals in different matrices.

Application Analyte Extraction method Matrix LOD/LOQ (ng/ml) Recovery Analysis method References
Environmental Antioxidants, UV filters, and fragrances SPME(PDMS) Tap water 5–8,500 nr GC-MS Basaglia et al. (2011)
Estriol, estradiol, ethynylestradiol, estrone, progesterone, medroxyprogesterone, levonorgestrel, and norethindrone SBSE Water (tap water and raw 0.5 × 10–3–1.0 556–96% MS Vo Duy et al. (2012)
Wastewater
Triclosan, triclocarban, and their four related transformation products SPME Water 0.06–0.21 81.54–102.32% HPLC-DAD Shen et al. (2012)
0.12–0.73
Triclosan and bisphenol-A SPME (CW/TPR) Tap, river and 1 71–111 HPLC-DAD Kim et al. (2013)
Chlorophenols and mefenamic acid Wastewater 2–9
Gemfibrozil 3
Steroids SPME (PDMS/DVB) Local source water 30–2,000 84.9–103% GC-MS/MS Chopra et al. (2014)
Mesterolone
Methandriol
Estrone
Estradiol
Androstenedione
Eticholan-3–17-one
DES
Prasterone
Sulfonamides, sulfacetamide, sulfadiazine, sulfathiazole, sulfamethazine, sulfamethoxypyridazine, and sulfamethoxazole MEPS(C8) Wastewater 5–200 88–109% HPLC-DAD Salami and Queiroz, (2014)
Flufenamic acid and mefenamic acid SPME Water 6 × 10−5–1.24 × 10−3 85.1–110.8% GC-MS Huang et al. (2015)
Flurbiprofen 2.2 × 10−4–4.13 × 10−3
Clofibrate
Ketoprofen
Naproxen
Tolfenamic acid
Gemfibrozil
Estriol, 17β-estradiol, testosterone, ethinylestradiol, estrone, progesterone, and mestranol SPME-fiber Water nr 75.6–116% HPLC Liao et al. (2016)
Androgens and progestogens FSPE (sol-gel PTHF) Water, urine 1.7 × 10−3–0.264 (water samples) 83.8–103.9% water UHPLC–MS/MS Guedes-Alonso et al. (2016)
Norethisterone 8.9 × 10−3–0.132 (urine samples) 81.9–120% urine
Norgestrel
Megestrol acetate
Progesterone
Boldenone
Nandrolone
Testosterone
DHEA
Androsterone
Androstenedione
Penicillins (penicillin G, penicillin V, oxacillin, cloxacillin, dicloxacillin, and nafcillin) SPME (Al-MOF) River water 0.06–0.26 80.8–90.9% in water LC–MS or LC–UV Lirio et al. (2016)
81.1–100.7% in milk
Abacavir SPME-fiber Surface waters and wastewater 0.010–0.013 88–99% LC-MS Terzopoulou et al. (2016)
0.033
Chlorophenols and eleven estrogenic compounds SPME Surface water 8.8 × 10−3–42.9 × 10−3 69–108% GC-MS Yuan et al. (2017)
β-Estradiol SBSE Water nr 71.4–83.2% Suazo et al. (2017)
3-(4-metylbenzylidene)camphor
Carbamazepine
Ibuprofen
2,4-dihidroxybenzophenone
Triclosan SPME-Fiber (PDMS) Seawater 0.111, 0.177, 0.088 nr LC-MS/MS Santos et al. (2018)
Bisphenol A
17α-Ethynylestradiol
4-Chloro-1-naphthol SBSE Wastewater, pool water 0.034 87.4–141.3% HPLC Jillani et al. (2020)
0.400
Biological (fluids and tissues) NSAIDs MEPS (C18) Plasma, urine 30–100 nr HPLC-PDA Locatelli et al. (2014)
Furprofen, indoprofen, ketoprofen, fenbufen, flurbiprofen, indomethacin, and ibuprofen
Selected estrogens FSPE (sol-gel PTHF) Urine 0.036 88.7–98.0% HPLC-FLD Kumar et al. (2014)
α-17-ethynylestradiol 0.020
β-Estradiol 0.042
α-Bisphenol A
Ciprofloxacin and levofloxacin, two fluoroquinolones MEPS (C18) Sputum 17–50 >80% HPLC-PDA Locatelli et al. (2015)
Cocaine, amphetamines, natural and synthetic opioids, and hallucinogens (AMP, MAMP, MDA, MDMA, and MDEA) MEPS Oral fluid 1, 1, 1, 0.5 & 0.5 >60% LC-MS/MS Montesano et al. (2015)
Estriol, 17β-estradiol, testosterone, ethinylestradiol, estrone, progesterone, and mestranol SPME-fiber Urine nr 75.6–116% HPLC Liao et al. (2016)
Benzodiazepines FSPE (sol-gel PEG) Blood serum 30 nr HPLC Samanidou et al. (2016)
10
Abacavir SPME-fiber Urine 43.9 × 10−3 88–99% LC-MS Terzopoulou et al. (2016)
12 azole drugs (bifonazole, butoconazole, clotrimazole, econazole, itraconazole, ketoconazole, miconazole, posaconazole, ravuconazole, terconazole, tioconazole, and voriconazole) MEPS (C18) Plasma, urine 0.23 and 0.37 88.5–99.2% HPLC-DAD Campestre et al. (2017)
Trans,trans-muconic acid MIP-MEPS Urine 50 89.8–91.6% HPLC-UV Soleimani et al. (2017)
15
Statins MEPS (C18) Plasma 10–20 nr UHPLC-MS/MS Ortega et al. (2017)
Drugs of abuse MEPS C8/SCX Plasma 5–10 80–104% UPLC Fernández et al. (2017)
Morphine
Methylone
6-AM
Mephedrone
BEG
Cocaine
MDPV
Cocaethylene
EDDP
Methadone
Voriconazole SPME-MS Human plasma 3–6 nr Coated blade spray-MS Tascon et al. (2017)
Ciprofloxacin FSPE (sol-gel Carbowax® 20 M) Whole blood Plasma 250 (10) nr HPLC-PDA Kabir, et al. (2018)
Sulfasalazine Urine 110 (30)
Cortisone 100 (30)
Cyclosporine SPME-MS Whole blood 3.0 nr Coated blade spray-MS/MS Gomez-Ríos et al. (2018)
Tacrolimus Whole blood 0.3
Sirolimus Whole blood 1.0
Everolimus Whole blood 0.3
losartan and valsartan SBSE Human plasma 7.0 98–117% LC-MS Babarahimi et al. (2018)
27.0
Methylphenidate SPME Human heparin plasma nr nr TD-ESI/MS Wang et al. (2018)
Doxorubicin SPME Lung tissue 103.2% LC-MS/MS Roszkowska et al. (2018)
Antibiotics and their metabolites (amoxicillin, cefotaxime, ciprofloxacin, clindamycin, metronidazole, amoxycilloic acid, 4-hydroxyphenyl glycyl amoxicillin, desacetyl cefotaxime, 3-desacetyl cefotaxime lactone, ciprofloxacin N-oxide, N-demethyl clindamycin, clindamycin sulfoxide, and hydroxy metronidazole SPME-C18 fiber Human whole blood and tissue samples 28–45 89.29–98.39% HPLC-QqQ-MS Szultka-Mlynska et al. (2018)
85–135
NSAIDs (ibuprofen, diclofenac, naproxen, and nalidixic acid) SPME- Fe3O4/Cu3(BTC)2 MOF Human urine, serum, plasma, and tablets 0.03–0.05 94.0–102.0%. HPLC Mirzajani et al. (2019)
0.12–0.18
Methamphetamine SPME Hair 0.067 90.2–95.8% LC-MS Meng et al. (2020)
Amphetamine 0.067
Ketamine 0.067
Norketamine 0.067
Perphenazine, chlorpromazine, chlorprothixene, promethazine, and trifluoperazine Hollow fiber SPME Human whole blood and urine 0.025, 0.0125, 0.025, 0.025 and 0.0125 46.4–96.6% (blood) UPLC-MS/MS Li et al. (2020)
65.2–101.9% (urine)
Alprazolam and amitriptyline DI-SPME Human blood and bone marrow 1.87–10.45 nr LC-TOFMS Majda et al. (2020)
Bromazepam and carbamazepine, citalopram 5.60–31.35
Clonazepam,clorazepate, desipramine, and diazepam
Estazolam, flunitrazepam, and fluoxetine
Imipramine, lorazepam, lormetazepam, midazolam, nitrazepam, nordazepam, and nortriptyline
Paroxetine, prazepam, and temazepam
Tetrazepam, venlafaxine, and zolpidem
4-chloro-1-naphthol SBSE Human urine 0.034 87.4–141.3% HPLC Jillani et al. (2020)
0.400
Tranexamic acid SPME-Thin film Human plasma and urine 10000–25000 nr LC-MS/MS Looby et al. (2021)
Others (food, animal tissue, in vivo, dosage forms) Melatonin and other antioxidants MEPS (C18) Foodstuff 0.02 nr HPLC-FLD Mercolini et al. (2012)
Carvedilol enantiomers SBSE Pharmaceutical dosage forms 8 (R) and 11 (S) 98–103% HPLC Taraji et al. (2015)
25 (R) and 50 (S)
Clenbuterol SPME Pork 3.6 × 10−6 97.4–105.7%. GC/MS Ye et al. (2016)
Salicylic, 3-methyl salicylic, 4-methyl salicylic, acetylsalicylic, and benzoic acids SPME Fruits and vegetables 2–28 78.0 ± 1.3% HPLC Aresta and Zambonin, (2016)
7–95
Neurotransmitters SPME Macaque brain 25–20,000 80–100% LC-MS/MS Lendor et al. (2019)
98 pharmaceutical analytes SPME Bovine tissue (0.25–3X, where X corresponds to the MRL for each target analyte) nr SPME-DART-MS/MS Khaled et al. (2020)

nr: not reported.