D-735

Arginine and Methionine Determination by HPLC coupled with UV-Vis Spectroscopy

Section D — Laboratory Operations and Specifications Revision 5 8 pages

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1.0 Purpose 
 
 The purpose of this procedure is to describe a method for the quantitative analysis and
 identification of Arginine and Methionine in finished products and raw materials using HPLC
 
 and UV/VIS spectrophotometry. 
 
 2.0 Scope 
 
 This procedure applies to the quantification and identification of Arginine and Methionine. Some
 
 excipients and dietary ingredients used in the finished products can interfere with the analysis of
 Arginine and Methionine. Other wavelengths can be used to measure area if interferences are
 
 present. 
 
 3.0 Responsibility 
 
 3.1 It is the responsibility of QC and Analytical Chemists to follow this procedure.
 
 3.2 It is the responsibility of QC Laboratory Management to implement this procedure and
 
 to ensure that the procedure is being followed. 
 
 3.3. It is the responsibility of QC Laboratory Management/Analytical Development to keep
 
 the procedure current with Ion Labs practices. 
 
 4.0 Definitions 
 
 4.1 ACN - Acetonitrile 
 
 4.2 HCl— Hydrochloride 
 
 4.3. HeO- Deionized water (> 18.2 MQ-:cm) 
 
 44 QC-— Quality Control 
 
 4.5 CofA — Certificate of Analysis 
 
 
 

[SOP 

 Standard Operating Procedure SOP No Rev 
 Arginine and Methionine Determination by HPLC D-735 Page 2 of 8 
 coupled with UV/VIS Spectroscopy 
 
 5.0 References 
 
 Sm MV-LAB-14-012, Protocol, Open validation protocol for amino acids and amines.
 
 5.2. MV-LAB-13-040, Protocol, L-Arginine Determination by HPLC 
 
 5.3. D-793, SOP, Cryogenic Grinding of Chewable Gels 
 
 6.0 Reagents, Supplies, Glassware and Equipment 
 
 6.1 Reagents: all reagents are HPLC grade or better. 
 
 6.1.1 H20 
 
 6.1.2. ACN 
 
 6.1.3 Ammonium Acetate 
 
 6.1.4 Arginine reference standard (HCL or a-ketoglutarate) 
 
 6.1.5 Methionine reference standard 
 
 6.2 Supplies and Glassware 
 
 6.2.1 HPLC vials, 12mm X 32mm with screw cap enclosures w/ septa 
 
 6.2.2 Mobile phase containers 
 
 6.2.3 Volumetric glassware as required by standard and sample preparations
 
 6.2.4 50 mL and 100 mL beakers 
 
 6.2.5 Tips for adjustable pipettes 
 
 6.2.6 Micro centrifuge tubes 
 
 6.2.7 Plastic luer lock syringe 
 
 6.2.8 0.2 or 0.45um nylon syringe filters 
 
 6.2.9 Screw cap vials (scintillation) 
 
 6.2.10 Weigh boats 
 
 
 

[SOP 

 Standard Operating Procedure SOP No Rev 
 Arginine and Methionine Determination by HPLC D-735 Page 3 of 8 
 coupled with UV/VIS Spectroscopy 
 
 6.3 Equipment 
 
 6.3.1 Suitable gradient HPLC system consisting of a pump, autosampler, column oven
 and UV detector with a chromatographic data handling system 
 
 6.3.2 Analytical Balance 
 
 6.3.3. Vortex 
 
 6.3.4 Stir Plate 
 
 6.3.5 Wrist action shaker 
 
 6.3.6 Micro-centrifuge 
 
 6.3.7. Adjustable pipettes 
 
 7.0 Procedure 
 
 7.1. Mobile Phase and Buffer Preparation 
 
 7.1.1 Mobile Phase A —-20 mM Ammonium acetate in H2O 
 
 7.1.1.1 Transfer 1.54 g of ammonium acetate to a 1-L bottle. 
 
 7.1.1.2 Add 1000 mL H20, and mix well. 
 
 7.1.2 Mobile Phase B - ACN 
 
 7.1.3 Diluent - Mobile Phase A 
 
 7.2 Standard Preparation 
 
 7.2.1 All Standards are prepared by weighing no less than the minimum weight of the
 
 analytical balance. Dissolve standard in two-thirds its final volume in an
 appropriately sized volumetric flask using Diluent. Mix on the wrist action shaker
 
 for 30 minutes then inspect to ensure complete dissolution. Once standard is fully
 dissolved, bring standard to final volume before using. 
 
 7.2.2 To manage large volumes, the standard can be initially prepared at a higher
 
 concentration and further diluted into the linear range using Diluent. Dilutions
 
 
 

[SOP 

 Standard Operating Procedure ~SOPNo | Rev 
 Arginine and Methionine Determination by HPLC D-735 5 | Page 4 of 8 
 coupled with UV/VIS Spectroscopy 
 
 can be made using volumetric glassware and‘ci ac justable pipettes. . ‘ir al dilutions
 can be prepared in HPLC vials. 
 
 7.2.3 Specific standard concentrations will approxii aa e the concentraticn :xpected to
 
 be found in the product being tested based on th: sample dilution :n calculated
 
 from the label. 
 
 7.3. Sample Preparation 
 7.3.1 Specific sample testing details are provided in ea sh products profil». : fa specific
 
 testing details section is not available, then fi llow preparation pi »cedure as
 
 described below, maintaining concentration w th n the linear range li: ted below.
 
 7.3.2 The linear range of the method for arginine is 0 | mg/mL — 1.6 rog/i aL. HCI or
 ketoglutarate salt. 
 
 7.3.3. The linear range of the method for methionine is 0.005 mg/mL — 0 81 1g/mL.
 
 7.3.4 For raw materials: weigh no less than 20 mg in:0 1 suitably sized vc lw aetric flask
 
 of no less than 25 mL volume to generate an < nz yte concentration tk at is within
 
 the validated linearity range. Add Diluent t» ‘/3 of the flask vol une, shake
 mechanically for 30 min, and dilute to volume u: ing Diluent.
 
 7.3.5 For solid and liquid dose finished products: 20 ribine and homo, er ize no less
 
 than ten dosage units. Based on the label clairc at d fill weight (cap: ul +s), serving
 size (powders) or tablet weight per dose, weig 110 less than 50 mg o/ the pooled!
 
 dosages into a suitably sized volumetric flask of no less than 25 n L :o generate
 
 an analyte concentration that is within the val: da ed linear range. 4 d< Diluent to
 2/3 of the flask volume, shake mechanically fo 30 min, and dil tte to volume:
 
 using Diluent. 
 
 7.3.6 For chewable gels (gummies), homogenize at lei st 10 dosage unit a cording tc
 the procedure outlined in D-793 Cryogenic Grin ling of Chewable Se ls. Quickly
 
 weigh a portion of the pooled and homogenize d sages into a beaki r. Jse severa
 small portions of Diluent to completely trans/2r ‘he sample into a su tably sizec
 
 
 

[SOP 

 Standard Operating Procedure SOP No Rev 
 D-735 
 Arginine and Methionine Determination by HPLC Page 5 of 8 
 coupled with UV/VIS Spectroscopy 
 
 volumetric flask to generate an analyte concentration that is within the validated
 linear range. Add Diluent to 2/3 of the flask volume, shake mechanically for 30
 
 min, and dilute to volume using Diluent. 
 
 7.3.7 To manage large volumes, the sample can be initially prepared at a higher
 concentration and further diluted into the linear range using Diluent. Dilutions
 
 can be made using volumetric glassware and/or adjustable pipettes. Dilutions can
 
 be prepared in HPLC vials 
 
 7.3.8 If particulates remain in the final sample preparation, a portion may be centrifuged
 at 10,000 rpm for 5 min prior to HPLC analysis. Alternatively, the sample may
 
 be filtered through a 0.45 um membrane discarding the first 3-4 mL.
 
 7.4 Test Conditions 
 
 7.4.1 Gradient-Isocratic 
 
 7.4.1.1 Time %A %B 
 
 0.00 98 Z 
 
 8.00 98 az: 
 
 7.4.2 Column- Acclaim 120 C18, 5 um, 4.6 X 250 mm or equivalent 
 
 7.4.3 Flow Rate- 1.0 mL/min 
 7.4.4 UV detection- Arginine: 206 nm, Methionine: 210 nm 
 
 7.4.5 Injection volume- 20 uL 
 
 7.4.6 Column Temperature- 40 °C 
 
 7.4.7. Recommended 3-D Spectral Range- 200 nm to 300 nm 
 75 Retention Times 
 
 7.5.1 Arginine: 2.7 min 
 
 7.5.2 Methionine: 4.1 min 
 7.6 Recommended Sequence 
 
 7.6.1 Make at least 2 injections of a Blank (Diluent). 
 
 
 

[SOP 

 Standard Operating Procedure SOP No | Rev 
 Arginine and Methionine Determination by HPLC D-735 5 Page 6 of 8 
 coupled with UV/VIS Spectroscopy 
 
 7.6.2 Make five injections of the Working Standard. 
 
 7.6.3 Make a single injection of each Sample Preparation. 
 
 7.6.4 Make a single injection of the Working Standard after every six samples and at
 the end of the run. 
 
 7.7 System Suitability 
 
 7.7.1. %RSD of five consecutive injections of the Working Standard is NMT 5.0%.
 
 7.7.2 %RSD of all injections of the Working Standard is NMT 5%. 
 
 7.8 Column Rinse and Storage 
 
 7.8.1 Rinse the column with at least 15 mL of H2O/ACN (90/10). 
 
 7.8.2 Rinse the column with at least 15 mL of H2O/ACN (10/90). 
 
 7.8.3 Store the column in H20/ACN (10/90). 
 
 7.9 Example calculations for determining finished product % label or raw material % purity
 
 7.9.1 %assay o = x R :. u x gy Wh V a e t e a t a h 4 x Bent K « a 8S 100
 
 Ru Sample peak area 
 
 Rs; Mean standard peak area 
 
 Wtstq Weight of reference standard in mg 
 
 Vaca Volume of the standard preparation accounting for dilutions in mL
 
 P Purity of the reference standard in decimal format 
 
 SA Sample amount in mg 
 
 Vspt Volume of the sample preparation accounting for dilutions in mL
 
 SS Serving size: Weight of a single dosage unit in mg, or 1 for raw
 
 materials. 
 
 LA Label amount in mg per dose or 1 for raw materials 
 
 
 

[SOP 

 Standard Operating Procedure SOP No | Rev 
 Arginine and Methionine Determination by HPLC D-735 5 Page 7 of8 
 coupled with UV/VIS Spectroscopy 
 
 8.0 Example Chromatography and UV Spectra 
 
 8.1 Methionine Chromatogram 
 22AS013 
 110 
 100- 
 90- 
 80- 
 70 
 607 
 507 
 40- 
 307 
 20° 
 105 
 O74 
 -10- 
 UAm 
 1354 
 eninoihteM-L 
 05 1 15 2 25 #3 35 4 #45 #5 +55 #6 65 7 75 8 
 Time [min] 
 8.2. Methionine UV Spectrum 
 L-Methionine - 3.929 (2023-03-28 13-08-25-04-00-03-1001.dx) 
 100: 
 904 
 80+ 
 704 
 60+ 
 40- 
 307 
 20+ 
 104 
 oy 2d0 asd 260. -280.~+«300”~«320~««340”~««380”~=CSC«C«SC«SC«MOSCSCABOSCSOO S520 B40 S80) 580600
 nm 
 
 
 

[SOP 

 Standard Operating Procedure SOP No | Rev 
 Arginine and Methionine Determination by HPLC D-735 5 | Page 8 of8 
 coupled with UV/VIS Spectroscopy 
 
 8.3 Arginine Chromatogram 
 
 19AS029 
 0 o 
 sy 
 500- = 
 450} Be 
 400+ = 
 350+ 
 ~ 3004 
 = 2504 
 2007 
 150- 
 100; ae 
 507 f 3 8 
 2 ee 
 0 
 o5 4 16 2 26 3 35 4 45 5 55 65 7 75 8 
 Time [min] 
 8.4 Arginine UV Spectrum 
 - L-Arginine - 2.599 (2023-05-01 14-35-17-04-00-03-r002.dx) 
 90- 
 80+ 
 70+ 
 60+ 
 ® 504 
 40- 
 30; 
 204 
 104 
 2b 22 “ 0 — 240 260 260. 300 320 340 360 380 400 420 440 460 480 520 540 560 580 600
 nm 
 
 9.0 Revision History 

| Rev | Date | Description of Changes | CCR # | By |
|-----|----------|------------------------|-------|----|
| 2 | 01/06/15 | Updated SOP format. Added Methionine. | 15-0007 | X. Shao |
| 3 | 01/02/19 | Scheduled review: updated SOP format, stability requirement, weight requirement, and number of pooled tablets. Updated for consistency with current methods. Added system | 19-0009 | J. Maignan |
| 4 | 03/10/22 | suitability section. Added recommended sequence. Added CC- column rinse and storage. Removed unnecessary information and align with current SOP format. Added instruction to follow test details containing | 22-0108 | S. Sassman |
| 5 | 05/05/23 | product specific sample preparation, add specific sample prep CC- instructions for different dosage forms. Added example chromatography and spectrum. Changed logo. | 23-0231 | S. Sassman |