D-1024

Determination of Mannose by HPLC-UV

Section D — Laboratory Operations and Specifications 11 pages

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1.0 Purpose in absences of f MieMlael e Mo Motley‘, 4 SM 2I-0ct?-M02—
 
 The purpose of this procedure is to define the method for the determination of mannose in raw
 
 materials and finished products by HPLC/UV. 
 
 2.0 Scope 
 
 This procedure applies to the determination of mannose by HPLC/UV in the QC laboratory at
 
 HBI Ion Labs. 
 
 3.0 Responsibility 
 
 3.1 It is the responsibility of QC Chemists to follow this procedure. 
 
 3.2 It is the responsibility of QC Laboratory Management to ensure that this procedure is
 
 being followed. 
 
 3.3 It is the responsibility of QC Laboratory Management and/or Analytical Development to
 
 keep this procedure aligned with current practices. 
 
 4.0 Definitions 
 
 4.1 HPLC/UV — High Performance Liquid Chromatography with Ultraviolet Detection
 
 4.2 QC -— Quality control 
 
 4.3 PMP — 3-methyl-1-phenyl-2-pyrazoline-5-one 
 
 4.4 | HCl—Hydrochloric acid 
 
 
 

[SOP D-102 | Page 2 of 11]

 Standard Operating Procedure SOP No Rev Page 
 D-1024 
 Determination of Mannose by HPLC/UV 2 of 11 
 
 4.5 NaOH - Sodium hydroxide 
 
 4.6 | Hs3POa— Phosphoric acid (~85%) 
 
 4.7 | K2HPOs - Potassium phosphate dibasic 
 
 4.8 | HeO — Deionized water (>18MQ-cm) 
 
 4.9 DAD — Diode array detector 
 
 4.10 ACN - Acetonitrile 
 
 4.11 MeOH - Methanol 
 
 5.0 References 
 
 5.1 PRTCL-24-0015, Protocol, Validation of a Method for the Determination of Mannose by
 
 HPLC/UV. 
 
 5.2. Gonzalez NM, Fitch A., Al-Bazi J. (2020) Development of a RP-HPLC method for the
 
 determination of glucose in Shewanella oneidensis cultures utilizing 1-pheyl-3-methyl-
 5-pyrazolone derivatization, PLoS ONE 15(3). 
 
 5.3 D-793, SOP, Cryogenic Grinding of Chewable Gels 
 
 6.0 Supplies 
 
 6.1 Chemicals 
 
 6.1.1 D-(+)-Mannose and D-(-)-Ribose reference standards 
 
 6.1.2 ACN 
 
 6.1.3 PMP 
 
 6.1.4 0.5MHCI 
 
 
 

[SOP D-102 | Page 3 of 11]

 Standard Operating Procedure SOP No Rev Page 
 D-1024 
 Determination of Mannose by HPLC/UV 3 of 11 
 
 6.1.5 0.5 M NaOH 
 
 6.1.6 H3PQO, 
 
 6.1.7 KoHPO, 
 
 6.1.8 MeOH 
 
 6.1.9 Chloroform 
 
 6.1.10 H20 
 
 6.2. Glassware and Disposables 
 
 6.2.1 Volumetric glassware as required for standard and sample preparations
 
 6.2.2 HPLC vials, 2mL with screw-cap enclosures and septa 
 
 6.2.3 Tips for adjustable pipettes 
 
 6.2.4 0.45 um nylon or PVDF syringe filters 
 
 6.2.5 10-mL plastic syringes with luer lock fitting 
 
 6.3. Equipment 
 
 6.3.1 Suitable gradient HPLC system consisting of a pump, autosampler, column
 
 oven, and UV or DAD detector. 
 
 6.3.2 Analytical balance 
 
 6.3.3 pH meter 
 
 6.3.4 Water bath capable of maintaining temperature at 70°C 
 
 6.3.5 Wrist action shaker 
 
 
 

[SOP D-102 | Page 4 of 11]

 Standard Operating Procedure SOP No Rev Page 
 Determination of Mannose by HPLC/UV D-1024 : 4 of 11 
 
 6.3.6 Adjustable pipettes 
 
 7.0 Preparation of Mobile Phase, Extraction Solvent, Standards, Internal 
 
 Standards, and Samples 
 
 7.1 Mobile Phase A (15 mM K2HPOs, in H20) 
 
 7.1.1 Transfer 2.61 g of K2HPOs, to a suitable container. 
 
 7.1.2 Add 1000 mL of H20 and a stir bar. 
 
 7.1.3 Begin stirring and adjust to pH 7.2 using H3POs. 
 
 7.2... Mobile Phase B (ACN) 
 
 7.2.1 Use 100% ACN. 
 
 7.3 Internal Standard Solution (12.5 mg/mL D-(-)-Ribose in H20) 
 
 7.3.1. Accurately weigh and transfer about 625 mg of D-(-)-Ribose to a 50-mL
 
 volumetric flask. 
 
 7.3.2 Dissolve in and dilute to volume using H2O. 
 
 7.4 Derivatization Solution (0.5 M PMP in Methanol) 
 
 7.4.1. Accurately weigh and transfer about 870 mg of PMP to a 10-mL volumetric
 
 flask. 
 
 7.4.2 Dissolve in and dilute to volume using methanol. 
 
 
 

[SOP D-102 | Page 5 of 11]

 Standard Operating Procedure SOP No Rev Page 
 Determination of Mannose by HPLC/UV D-1024 : 5 of 11 
 
 7.5 Stock Standard (2.5 mg/mL D-(+)-Mannose + 2.5 mg/mL D-(-)-Ribose) 
 
 7.5.1 Accurately weigh and transfer about 62.5 mg D-(+)-Mannose into a 25-mL
 
 volumetric flask. 
 
 7.5.2 Add 5.0 mL of Internal Standard Solution. 
 
 7.5.3 Dissolve in and dilute to volume using H20. 
 
 7.6 Stock Sample Preparation (~2.5 mg/mL D-(+)-Mannose + 2.5 mg/mL D-(-)-Ribose)
 
 7.6.1 Specific sample testing details are provided in each products profile. If a
 specific testing details section is not available, then follow preparation
 
 procedure as described below, maintaining concentration within the linear range
 of this method. 
 
 7.6.2 The validated linear range of the method is 1 mg/mL — 5 mg/mL based on the
 concentration of mannose in the Stock Sample. The Stock Sample preparation
 
 must be within the linear range of the method. 
 
 7.6.3 Ensure that the sample is homogeneous prior to weighing. 
 
 7.6.3.1 For capsules, combine the fill material from at least 10 dosage units
 and homogenize in a mortar and pestle if necessary. 
 
 7.6.3.2 For tablets, combine at least 10 dosage units and homogenize in a
 
 mortar and pestle. 
 
 7.6.3.3. For chewable gels (gummies), homogenize at least 10 dosage units as
 
 outlined in D-793. 
 
 7.6.4 Based on the raw material manufacturer’s assay value or finished product label
 
 claim, accurately weigh and transfer a sufficient amount of sample to deliver
 about 125 mg of D-(+)-Mannose to a 50-mL volumetric flask. 
 
 
 

[SOP D-102 | Page 6 of 11]

 Standard Operating Procedure SOP No | Rev Page 
 Determination of Mannose by HPLC/UV D-1024 : 6 of 11 
 
 7.6.5 Add5.0 mL of methanol and swirl to completely wet the sample.
 
 7.6.6 Add 10.0 mL of Internal Standard Solution. 
 
 7.6.7. Add about 20 mL of H20. 
 
 7.6.8 Shake on a wrist-action shaker for 20 min. 
 
 7.6.9 Dilute to volume with H2O, and shake vigorously. 
 
 7.7. Derivatization Reaction and Cleanup (Option 1) 
 
 7.7.1 Transfer 1.6 mL of Stock Standard into a 15-mL glass centrifuge tube.
 
 7.7.2 Transfer 1.6 mL of Stock Sample into a separate 15-mL glass centrifuge tube.
 
 7.7.3 Add 1.6 mL of 0.5 NaOH to each of the standard/sample tubes.
 
 7.7.4 Vortex briefly to mix. 
 
 7.7.5 Add 1.6 mL of Derivatization Solution to each of the standard/sample tubes.
 
 7.7.6 Vortex briefly to mix. 
 
 7.7.7 Incubate in a water bath at 70°C for 90 min, shaking by hand every 30 min.
 
 7.7.8 Equilibrate to room temperature. 
 
 7.7.9 Add 1.6 mL of 0.5 M HCI to each of the standard/sample tubes.
 
 7.7.10 Add 2.0 mL of chloroform to each of the standard/sample tubes.
 
 7.7.11 Vortex for about 5 sec to mix well. 
 
 7.7.12 Right away vent sample to release pressure. 
 
 7.7.13 Repeat steps 7.7.11 — 7.7.12 until pressure stops building up.
 
 
 

[SOP D-102 | Page 7 of 11]

 Standard Operating Procedure SOPNo | Rev Page 
 Determination of Mannose by HPLC/UV D-1024 : 7 of 11 
 
 7.7.14 Centrifuge at 4000 rpm for 3 min to separate the layers. 
 
 7.7.15 Use a glass pipet to remove and discard the bottom (chloroform) layer.
 
 7.7.16 Repeat steps 7.7.10 — 7.7.15 twice for a total of3 washes. 
 
 7.8 Derivatization Reaction and Cleanup (Option 2) 
 
 Transfer 1.6 mL of Stock Standard into a 15-mL glass centrifuge tube.
7.8.1 7.8.2 Transfer 1.6 mL of Stock Sample into a separate 15-mL glass centrifuge tube.
 
 7.8.3 Add 1.6 mL of 0.5 NaOH to each of the standard/sample tubes.
 
 7.8.4 Vortex briefly to mix. 
 
 7.8.5 Add 1.6 mL of Derivatization Solution to each of the standard/sample tubes.
 
 7.8.6 Vortex briefly to mix. 
 
 7.8.7 Incubate in a water bath at 70°C for 90 min, shaking by hand every 30 min.
 
 7.8.8 Equilibrate to room temperature. 
 
 7.8.9 Add 1.6 mL of 0.5 M HCI to each of the standard/sample tubes.
 
 7.8.10 Quantitatively transfer reaction mixture from standard/sample tubes to separate
 
 separatory funnels with at least 2 mL of chloroform 
 
 7.8.11 Shake and vent well to release pressure, let layers separate
 
 7.8.12 Discard bottom (chloroform) layer 
 
 7.8.13 Repeat steps 7.7.11 — 7.7.12 with at least 2 mL of chloroform twice more for a
 
 total of 3 washes. 
 
 7.8.14 Transfer remaining (top) layer to scintillation vials 
 
 
 

[SOP D-102 | Page 8 of 11]

 Standard Operating Procedure SOP No Rev Page 
 Determination of Mannose by HPLC/UV D-1024 8 of 11 
 
 7.9 | HPLC Sample Preparation 
 
 7.9.1 Transfer 1.0 mL of each reaction mixture after chloroform washing into separate
 
 100-mL volumetric flask. 
 
 7.9.2 Dilute to volume using H20. 
 
 7.9.3 Filter a portion using a 0.45 um syringe filter (nylon or PVDF), discarding the
 first 2-3 mL before collecting a portion in an HPLC vial for analysis.
 
 7.10 Instrument Method Parameters 
 
 7.10.1 Column: Phenomenex Kinetex XB-C18, 4.6 x 150 mm, 2.6 um or equivalent
 
 7.10.2 Flow Rate: 1.0 mL/min 
 
 7.10.3 Run Time: 25 min 
 
 7.10.4 Gradient 
 
 Time (min) | %A %B 
 0.0 88 12 
 12.0 80 20 
 15.0 35 65 
 20.0 35 65 
 20.1 88 12 
 25.0 88 12 
 
 7.10.5 Injection Volume: 5 wl 
 
 7.10.6 Column Temperature: 30 °C 
 
 7.10.7 Wavelength: 245 nm 
 
 7.10.8 Suggested 3-D Spectral Range (for Identification): 210 nm — 400 nm
 
 
 

[SOP D-102 | Page 9 of 11]

 Standard Operating Procedure SOP No Rev Page 
 Determination of Mannose by HPLC/UV D-1024 I 9 of 11 
 
 7.11 Recommended Sequence 
 
 7.11.1 Make at least 1 injection of a Blank (H20). 
 
 7.11.2 Make 5 injections of the Working Standard. 
 
 7.11.3. Make a single injection of each Working Sample. 
 
 7.11.4 Make a single injection of the Working Standard after every six samples and at
 the end of the run. 
 
 7.12 System Suitability Requirements 
 
 7.12.1 The %RSD for five consecutive injections of Working Standard is NMT 3%.
 
 7.12.2 The %RSD for all injections of Working Standard is NMT 5%. 
 
 7.12.3 No significant (>0.5%) interference is present in the Blank injection.
 
 7.13. Column Wash and Storage 
 
 7.13.1. Wash the column at 1 mL/min with H2O/ACN (90/10). 
 
 7.13.2 Wash the column at 1 mL/min with H2O0/ACN (50/50). 
 
 7.13.3 Store the column in H20/ACN (50/50). 
 
 7.14 Example Calculation 
 
 Ru WtstaXP SS Von 
 % assay = R Ven x Spl. x TA x 100 
 
 Ruy Sample relative response 
 
 Rg Mean standard relative response 
 
 Wtetg Weight of reference standard in mg 
 
 
 

[SOP D-102 | Page 10 of 11]

 Standard Operating Procedure SOPNo | Rev Page 
 Determination of Mannose by HPLC/UV D-1024 . 10 of 11 
 
 Vsta Volume of the standard preparation accounting for dilutions in mL
 
 P Purity of the reference standard in decimal format 
 
 SS Serving size: Weight of a single dosage unit in mg or | for raw materials.
 
 Splwe Sample weight in mg 
 
 Vspl Volume of the sample preparation accounting for dilutions in mL
 
 LA Label amount in mg per dose or 1 for raw materials 
 
 8.0 Example Chromatograms 
 
 8.1 Blank 
 
 _ % 240208 Lectin Shield PRTCL-24-0015 #2 H20 UV_MS_4 WVL:245 am
 1| MAU 
 
 min 
 0.t6 T T T 2)T))OCOaStSt*~<CSs‘“aS:*~<“‘s=‘C S*“‘“C NGSC!;TM;‘“‘C#OSC;”C#*;‘CS‘COUNOGSC;*;‘C‘OC‘O“NS”!:”*;*~‘<« Rs tt (tit (KB
 8.2 Standard 
 
 467 - a 240205 Lectin Shield PRTCL.24-0015 #7 23AS056 UV_MS_4 WVL:245 am
 
 4G. - ‘ 
 
0.0 S&K ot
 
730.01 -

 esonnaM-7 
 PMPee 
371.11 -esobiR

 .PM 
 5 
 10.0 - 
 mu 
 “8,5 0 - .| 0 T T 2.T 0 T T T 40T T T T 6.T 0 T T T &¢T T T T 10.T 0 T T T 12T. 0 T T T 14T. 0 T T T 181. 6 T 2 T 18T. 0 T T T 20.T 0 T T T 22.T 0 T T T 24T 0 T 2616
 

[SOP D-102 | Page 11 of 11]

 Standard Operating Procedure SOP No | Rev Page 
 Determination of Mannose by HPLC/UV D-1024 . 11 of 11 
 
 8.3 Sample 
 487 - % 240208 Lectin Shield PRTCL-24-0015 #8 200462 UV_MIS_1 WVL:248 nm
 © i} maw 3 2 
 J o pn 
 40.04 - = 
 4 Py ‘ } = x & 
 a = i" 
 30.0- = a up 
 | a 4 = 
 20.0- ; = x 
 4 = 
 2 ‘a 
 = = 
 10.0- 
 A ‘as 
 4 op 
 6.0- ey | ene i aint | 
 1 min 
 “8.5 ° 0 . — 0 — T T 2. T 0 T T T 4G T T T T 60 T : y 7 8. T 6 ’ T y 10. T 0 T T r 12. T 0 T T 14 T . 0 ' * T 48. T 0 ’ 7 t 18. T 0 T TM—T 20. T 6 7 7 T 22. T 0 r " T 24 T 0 ? 25. 1 0
 9.0 Revision History 

| Rev | Date | Description of Changes | CCR # | By |
|-----|----------|------------------------|-------|----|
| 0 | 04/30/24 | New procedure. N/A S. Sassman Added use of separatory funnel as an acceptable method for 1OOL2> derivatization step 7.8. Added clarifying steps to 7.7. CC-25-0372 M. sutcey | - | - |