🇲🇾 NPRA — Pusat Kawalan Kualiti (PKKK)

◈ Seksyen Pengujian Produk & Kosmetik · Unit Penyaringan

Adulteration Screening Analysis Guides

Complete Step-by-Step SOP Workflows: PPI · Domperidone · EG/DEG GCMS · Steroids · Hydroquinone · Lovastatin

Execution-ready operating procedures covering sample preparation, extraction protocols, chromatographic & spectrometric methods, SST verification criteria, batch sequences, and official reporting.

HPLC · Isocratic

Proton Pump Inhibitors (Omeprazole & Lansoprazole) Identification

PKKK/300/UP/025 · Fail Arahan Kerja F03 · Borang UP/005
ColumnZorbax SB C18 (250 × 4.6 mm, 5 µm)
Mobile PhaseIsocratic: 65% Buffer pH 7.6 : 35% ACN
Flow & Temp1.0 mL/min @ 30 °C (Sampler: 4 °C)
DetectorPDA @ 280 nm (Scan 190–400 nm)
Inj Vol & Time15 µL · Run Time: 20.0 minutes
Buffer Recipe25 mM di-Sodium Hydrogen Phosphate (Na₂HPO₄), pH 7.6
STEP-BY-STEP PROCEDURE
1. Reagent & Standard Preparation (Para 6.1 – 6.3)

Buffer 25 mM Na₂HPO₄ pH 7.6: Dissolve 3.55 g of Anhydrous di-Sodium Hydrogen Phosphate in 1000 mL Ultrapure water. Adjust pH to 7.6 using dilute Orthophosphoric acid (H₃PO₄). Filter through 0.45 µm nylon membrane filter and degas for 20 min.

Primary Stock Standard (1.0 mg/mL): Accurately weigh 10.0 mg of Omeprazole and Lansoprazole RS into separate 10 mL volumetric flasks. Dissolve and make up to volume with Methanol.

Mixed Working Standard (0.05 mg/mL each): Pipette 0.5 mL of Omeprazole and 0.5 mL of Lansoprazole stock solutions into a single 10 mL volumetric flask. Make up to volume with Methanol.

LOD Solution (0.003 mg/mL): Pipette 0.6 mL of Mixed Working Standard into a 10 mL flask and make up with Methanol.

2. Sample Extraction & Preparation (Para 6.4)

Tablets / Capsules: Finely pulverize sample. Weigh 1.0 g of sample into a 50 mL centrifuge tube.

Extraction Solvent: Pipette 20.0 mL of Methanol into the tube. (*Note: For softgels, use 20.0 mL of Chloroform as soft capsule matrices do not dissolve in Methanol).

Extraction: Sonicate in ultrasonic bath for 15 minutes. Centrifuge at 3000 rpm for 10 minutes.

Filtration: Filter supernatant through 0.45 µm PTFE / Nylon syringe filter into HPLC vial.

3. Batch Sequence of Injection (Table 3)

Vial 1: Blank (Methanol) [1x]Vials 2–7: Working Standard 0.05 mg/mL [6x for SST]Vial 8: LOD Solution [1x]Vial 9: Blank [1x]Vials 10–11: Sample 1 (Inj A & B) [2x]Vials 12–19: Samples 2 to 5 with BlanksVial 20: LOD Solution [1x IQC Bracket]End: LOD Solution [1x].

4. System Suitability & Identification Criteria (Para 6.5.6 – 6.5.7)

SST: Retention Time %RSD ≤ 2.0%, Tailing Factor T ≤ 2.0, Theoretical Plates N ≥ 2000.

Identification: Positive if Sample RT matches Standard RT (±2%) AND PDA UV spectrum (190–400 nm) similarity index > 0.999.

Confirmation: Fresh re-extraction by Second Analyst on separate date + GCMS confirmation (PKKK/300/UP/004 or 017).

HPLC · Gradient

Domperidone Adulterant Identification

PKKK/300/UP/027 · Fail Arahan Kerja F03 · Borang UP/005
ColumnZorbax Eclipse Plus C18 (150 × 4.6 mm, 5 µm)
Mobile PhaseGradient: 20 mM KH₂PO₄ pH 3.0 : ACN
Flow & Temp1.0 mL/min @ 40 °C (Sampler: 4 °C)
DetectorPDA @ 284 nm (Scan 190–400 nm)
Inj Vol & Time10 µL · Run Time: 20.0 minutes
Buffer Recipe20 mM Potassium Dihydrogen Phosphate (KH₂PO₄), pH 3.0 with H₃PO₄
STEP-BY-STEP PROCEDURE
1. Reagent & Standard Preparation (Para 6.1 – 6.3)

Buffer 20 mM KH₂PO₄ pH 3.0: Dissolve 2.72 g of Potassium Dihydrogen Phosphate in 1000 mL Ultrapure water. Adjust pH to 3.0 with Orthophosphoric acid. Filter (0.45 µm) and degas for 20 min.

Domperidone Stock (1.0 mg/mL): Accurately weigh 10.0 mg Domperidone RS into 10 mL volumetric flask. Dissolve and dilute with Methanol.

Working Standard (0.05 mg/mL): Dilute 0.5 mL stock to 10 mL with Methanol.

LOD Solution (0.003 mg/mL): Dilute 0.6 mL working standard to 10 mL with Methanol.

2. Sample Extraction (Para 6.4)

• Weigh 1.0 g of tablet/capsule/liquid sample into 50 mL centrifuge tube.

• Add 20.0 mL Methanol (or Chloroform for softgels). Sonicate for 15 minutes, centrifuge at 3000 rpm for 10 minutes. Filter through 0.45 µm Nylon filter.

3. Gradient Program (Table 2)
Time (min)Buffer pH 3.0 (%)Acetonitrile (%)Flow
0.01 – 1.9990 %10 %1.0 mL/min
2.00 – 3.9970 %30 %1.0 mL/min
4.00 – 7.9950 %50 %1.0 mL/min
8.00 – 11.9940 %60 %1.0 mL/min
12.00 – 14.0930 %70 %1.0 mL/min
14.10 – 20.0090 %10 % (Re-equilibration)1.0 mL/min
4. SST & Identification Acceptance

• SST: Retention Time %RSD ≤ 2.0%, Tailing T ≤ 2.0, N ≥ 2000.

• Positive Match: Sample RT within ±2% of Domperidone RS & UV Spectrum similarity > 0.999.

GCMS · SIM Quantitation

Diethylene Glycol (DEG) & Ethylene Glycol (EG) in Medicinal Syrups

PKKK/300/UP/034 · Fail Arahan Kerja F03 · Borang UP/009
ColumnBP20 Wax (30 m × 0.25 mm × 0.25 µm)
Carrier GasHelium @ 0.65 mL/min (Linear Vel: 30 cm/s)
InjectorSplit 20:1 @ 250 °C · Inj Vol: 1.0 µL
MS ModeEI @ 70 eV · Source: 230 °C · Interface: 240 °C
Solvent Delay4.0 minutes (Methanol off)
USP / NPRA LimitNot More Than 0.10 % v/v for EG and DEG
STEP-BY-STEP PROCEDURE
1. Standards Preparation & SIM Ion Tables (Para 6.3 & Tables 1–3)

Mixed Standard Stock (EG ~222.7 µg/mL & DEG ~223.7 µg/mL): Prepared in Methanol.

5-Level Calibration Curve:

  • Level 1 (LOQ): 6.01 µg/mL EG / 6.04 µg/mL DEG (135 µL stock ➔ 5 mL)
  • Level 2: 8.01 µg/mL EG / 8.05 µg/mL DEG (180 µL stock ➔ 5 mL)
  • Level 3 (SST): 10.02 µg/mL EG / 10.06 µg/mL DEG (225 µL stock ➔ 5 mL)
  • Level 4: 12.02 µg/mL EG / 12.07 µg/mL DEG (270 µL stock ➔ 5 mL)
  • Level 5: 14.02 µg/mL EG / 14.09 µg/mL DEG (315 µL stock ➔ 5 mL)
  • LOD Solution: 2.0 µg/mL (45 µL stock ➔ 5 mL)

SIM Ions:

Ethylene Glycol (EG) [RT 4.5–11.0 min]: Target Quant: m/z 31; Qualifiers: m/z 33, m/z 62.
Diethylene Glycol (DEG) [RT 11.0–20.0 min]: Target Quant: m/z 45; Qualifiers: m/z 75, m/z 31.

2. Sample Preparation for Medicinal Syrups (Para 6.4)

1. Accurately pipette 100 µL of medicinal syrup sample into a 10 mL volumetric flask.

2. Add HPLC grade Methanol, dissolve, and make up to the 10.0 mL mark.

3. Vortex thoroughly for 30 seconds. Transfer into GC autosampler vial for injection.

3. GC Oven Temperature Program (Table 2)

• Initial: 100 °C (hold 1.0 min)
• Ramp 1: 10.0 °C/min to 130 °C (hold 7.0 min)
• Ramp 2: 20.0 °C/min to 240 °C (hold 3.0 min)
• Post-run: 20.0 °C/min to 250 °C (hold 3.0 min). Total Time: 23.0 min.

4. System Suitability & Assay Calculation Formula

SST (6 Injections of Level 3 Standard): Peak Area %RSD ≤ 10.0%, Tailing Factor Tf ≤ 2.5, Theoretical Plates N ≥ 2000. LOD S/N ≥ 3, LOQ S/N ≥ 10.

Amount (%v/v) = Concentration from GCMS (µg/mL) × 10 mL 100 µL × 10⁴ × Density of Compound (g/mL)

Compliance Limit: EG ≤ 0.10% v/v and DEG ≤ 0.10% v/v. If > 0.10% v/v ➔ FAIL / OOS.

HPLC · Gradient LLE

Steroids (8-Compound Matrix) Screening

PKKK/300/UP/021 · PKKK/300/UP/014 · Borang UP/005
ColumnKinetex Phenyl-Hexyl 100Å (150 × 4.6 mm, 2.6 µm)
Mobile PhaseGradient: Ultrapure Water : Acetonitrile
Flow & Temp0.7 mL/min @ 40 °C (Cell: 40 °C)
DetectorPDA @ 240 nm (Scan 190–400 nm)
Inj Vol & Time10 µL · Run Time: 35.0 minutes
Target 8 SteroidsPrednisone, Prednisolone, Betamethasone, Dexamethasone, Triamcinolone acetonide, Hydrocortisone acetate, Cortisone acetate, Beta-17-valerate
STEP-BY-STEP PROCEDURE
1. Critical LLE Extraction (Adjust to pH 7.0)

• Weigh 1.5 g sample ➔ dissolve in 10–50 mL water ➔ sonicate 10–15 min ➔ adjust pH to exactly 7.0 with Ammonia/HCl ➔ extract 2× with 50 mL Chloroform (gentle rocking) ➔ evaporate bottom layer to dryness ➔ reconstitute in 3.0 mL Ethanol ➔ filter 0.45 µm.

2. Gradient Time Program (0.7 mL/min)

0.01–1.99 min (80% A : 20% B) ➔ 2.00–13.99 min (75% A : 25% B) ➔ 14.00–17.99 min (70% A : 30% B) ➔ 18.00–19.99 min (60% A : 40% B) ➔ 20.00–21.99 min (50% A : 50% B) ➔ 22.00–29.99 min (30% A : 70% B) ➔ 30.00–35.00 min (80% A : 20% B re-equilibration).

3. Positive Result Confirmation Protocol

• Positive match: Sample RT within ±2% of RS AND UV spectrum overlay similarity > 0.999.

Mandatory 2nd Analyst Protocol: Second analyst extracts new sample on different date at pH 7.0 ➔ Confirmation on GCMS (PKKK/300/UP/004 / 017).

HPLC · Isocratic ACM

Hydroquinone in Cosmetic Creams & Lotions Identification

PKKK/200/UP/001 · PKKK/300/UP/050 · Borang UP/001B & UP/X009
ColumnCosmosil 5 C18 AR-II (250 × 4.6 mm, 5 µm)
Mobile PhaseIsocratic: 99% Phosphate Buffer pH 2.5 : 1% MeOH
Flow & Temp0.9 mL/min @ 30 °C (Inj Vol: 20 µL)
DetectorPDA @ 280 nm (Scan 190–400 nm)
Buffer Recipe0.05 M Phosphate Buffer: 6.8 g KH₂PO₄ in 1000 mL, pH 2.5 with H₃PO₄
LOD & LimitLOD: 0.0005 mg/mL (0.002% w/w) · Banned in Cosmetics
STEP-BY-STEP PROCEDURE
1. Cosmetic Extraction Protocol

• Accurately weigh 1.0 g of cosmetic cream into a 50 mL centrifuge tube.

• Add 20.0 mL of Methanol. Sonicate at 40 °C for 15 minutes to melt cream matrices. Cool to room temperature.

• Centrifuge at 3500 rpm for 10 minutes. Filter supernatant through 0.45 µm PTFE syringe filter into HPLC vial.

2. SST & Identification Acceptance Criteria

Retention Time: Hydroquinone elutes at ~5.5 – 6.5 minutes.

SST: %RSD of 6 standard injections ≤ 2.0%, Tailing factor T ≤ 1.8.

Identification: Sample RT matches Hydroquinone RS (±2%) with UV spectral purity similarity > 0.999.

HPLC · Quantitative Assay

Determination of Lovastatin in Traditional Products

PKKK/200/UP/002 · Fail Arahan Kerja F03 · Borang UP/008A–G
ColumnThermo ODS Hypersil (200 × 4.6 mm, 5 µm)
Mobile PhaseIsocratic: 60% Acetonitrile : 40% 0.05% H₃PO₄ in Water
Flow & Temp1.8 mL/min @ 45 °C (Inj Vol: 10 µL)
DetectorPDA / UV @ 238 nm (Run Time: 6.0 min)
NPRA Limit≤ 1.00 % w/w AND ≤ 10.00 mg/day Daily Dose
SST Precision%RSD ≤ 2.0% (6 replicate injections) · R² ≥ 0.999
STEP-BY-STEP PROCEDURE
1. Standard & Sample Preparation

Stock Standard (100 µg/mL): Accurately weigh 10.0 mg Lovastatin RS in 100 mL volumetric flask with ACN.

Working Standard (20 µg/mL): Dilute 5.0 mL stock to 25 mL with Acetonitrile.

Sample Prep: Weigh accurately 20 pulverized tablets/capsules. Weigh portion equivalent to ~20 mg Lovastatin into 100 mL flask. Sonicate 20 min in ACN, filter 0.45 µm.

2. Quantitative Calculation Formula
%w/w Lovastatin = Sample Area × Std Conc (µg/mL) × Dilution (mL) × Purity (%) Std Area × Sample Weight (mg) × 1000
Daily Dose (mg/day) = %w/w × Average Unit Weight (mg) × Daily Recommended Units 100