Table 1.
Various chromatographic methods for determining adulterated drugs in herbal medicine.
| Analyte | Matrix | Method | Elution Type and Mobile Phase/Flow Rate | Column/Temperature | Detector | LOD/LOQ | % RSD/ Recovery |
Ref. |
|---|---|---|---|---|---|---|---|---|
| Sildenafil | Capsule, granule, herbal extract claimed for treatment of erectile dysfunction | TLC-SERS | Mobile phase: ethyl acetate-isopropanol-25% ammonia (45:5:2.6, v/v/v) | Stationary phase: 20 × 10 cm aluminium TLC plate |
Surface-enhanced Raman Spectroscopy (SERS) | LOD = 2 ng/spot | - | [4] |
| Sibutramine | Herbal slimming product | TLC-Densitometric | Mobile phase: toluene-diethylamine (10:0.3, v/v) | Stationary phase: aluminum TLC plates coated with silica gel 60 F254 with 250 μm thickness | Densitometric scanning at 227 nm with Camag® TLC Scanner III | LOD = 217.5 ng LOQ = 724.9 ng/spot |
Average recovery (%): 99.70 ± 1.22 RSD: <2% |
[12] |
| Sibutramine phenolphthalein, sildenafil |
Capsules (Sliming Bomb, Zotreem Plus, and Enjoy) |
HPLC-UV | Mobile phase SIB and PPH: potassium dihydrogen orthophosphate buffer (adjusted to pH 3 using o-phosphoric acid)/acetonitrile (40/60 v/v) Mobile phase SLD: acetonitrile–potassium hydrogen phosphate buffer (pH 3.2) adjusted using o-phosphoric acid (50/50 v/v) Flow rate: 1 mL/min |
Inertsil C18 Column (4.6 × 100 mm with 5 μm particle size) |
UV at 223 nm for SIB dan PPH and UV at 230 for SLD | - | RSD = 1.926% (SIB), 1.779% (PPH), 1.709% (SLD) Recovery: 98.64 ± 1.151 (SIB), 98.78 ± 1.537 (PPH), 99.11 ± 1.814 (SLD) |
[23] |
| Sildenafil, tadalafil, vardenafil hydrochloride | Capsule, cream, gel, etc. from 33 screened samples supplied by Public Authority of Customer Protection, Ministry of Health. | HPLC-MS-MS | Gradient elution. 0–2 min 5% B, 2–4 min 5% B, 4–7 min 40% B, 7–14 min 65% B, 14–18 min 90% B, 18–23 min 90% B, 23–23.5 min 5% B, and 23.5–27 min 5% B to equilibrate for the next injection (the total run time was 27 min). Mobile phase: A = 0.1% formic acid in water; B = 1% formic acid in 15% acetonitrile and 85% methanol flow rate: 0.3 mL min−1 |
Stationary phase: Poroshell 120 EC C18 column (3.0 ID × 100 mm length, 2.7 μm) (PC18) Temperature: 40 °C |
diode array | - | Coefficient variance CV = < 4% Relative error RE = < 3% |
[21] |
| Caffeine, chlorpheniramine, piroxicam, betamethasone, oxethazaine |
Capsule * | UPLC-QTOF-MS | Mobile phase: water with 0.1% formic acid (A) and acetonitrile (B) Elution type: gradient elution from 1% B to 70% B in 26 min with additional 2 min re-equilibration Flow Rate: 0.6 mL/min |
ACQUITY UPLC HSS T3 column (1.8 μm, 2.1 × 100 mm) Temperature: 45 °C | QTOF-MS with DIA as data acquisition | - | - | [24] |
| Sildenafil, tadalafil, aildenafil, sulfoaildenafil |
Pellets, capsules, tablets, or oral liquid, claimed functions of aphrodisiac, enhancement of sexual performance, physical fatigue relief or immunity enhancement | UHPLCQ-TOF HRMS | Gradient elution: began at 25% B for 2 min, then linearly ramped to 55% B within 11 min, and then ramped to 90% B in 1 min, and held at 90% B for 2.0 min mobile phase: A = 5 mmol/L ammonium acetate (adjusted pH to 3.4 with acetic acid) B = acetonitrile. Flow rate: 0.4 mL/min |
Column: Agilent SB-C18 RRHD column (100 mm × 3.0 mm, 1.8 mm) Temperature: 40 ℃. |
QTOF-MS/MS | LOD = 0.002–0.1 µg/g LLOQ = 0.005–0.25 mcg/g |
Recovery: 82.5–103.6%. RSD (Intra and inter-day): 0.4 to 13.6%. |
[9] |
| Fenfluramine, phenolphthalein, bumetanide, and sibutramine |
Slimming supplement: tea powder, capsule, tablets | Gtip SPE- UPLC–MS/MS | Gradient elution: initial 10% A, 4 min 50% A, 6 min 60% A, and 10 min 100% A. Total run time of 12 min. Mobile phase: Acetonitrile (A) and ultrapure water with 0.1% formic acid (B). flow rate: 0.40 mL/min |
Stationary phase: HaloTM fused-core C18 column (100 mm × 2.1 mm, 2.7 mcm) Temperature column 30 °C |
MS/MS | LOD = 1.8 ng mL−1) LOQ = 5.6 ng mL−1 |
Recovery = 82.9–95.2% RSD = <7.3% |
[25] |
| Amitriptyline acetaminophen, Ibuprofen, chlorzoxazone, sulfamethoxazole, tadalafil, and sildenafil |
83 Traditional Chinese medicines and 40 food supplements samples | GC-MS | Hydrogen as a carrier gas; 1.0 mL/min | A silica capillary column, Agilent HP-5 MS (30 m × 0.25 mm i.d. 0.25 μm film thickness); temperature programming | MS electron ionization | LOD = 10 to 1000 μg/g. | - | [26] |
* The detail herbal matrices available in the article.