Liquid chromatography with electrospray ionization mass spectrometry method for the assay of glucosamine sulfate in human plasma: validation and application to a pharmacokinetic study

Abstract

A liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method was developed and validated for the assay of glucosamine sulfate in human plasma. Plasma proteins were precipitated by acetonitrile, followed by vortex mixing and centrifugation. The supernatant was transferred and derivatized with phenyl iso-thiocyanate in acetonitrile at 60 degrees C for 40 min. Chromatographic separation was performed on a C(18) column (Inertsil ODS-3 150 x 2.1 mm i.d., 5 microm, JP) with a mobile phase gradient consisting of 0.2% acetic acid (aqueous) and methanol at a flow-rate of 0.3 mL/min. MS detection using electrospray ionization (ESI) as an interface was used in single ion monitoring mode to determine positive ions at m/z 297. This method was shown to be selective and sensitive for glucosamine sulfate. The limit of detection was 35 ng/mL for glucosamine sulfate in plasma and the linear range was 0.1-20 microg/mL in plasma with a correlation coefficient (r) of 0.9991. The relative standard deviations (RSDs) of intra-day and inter-day assays were 8.7-11.4 and 9.8-12.6%, respectively. Extraction recoveries of glucosamine sulfate in plasma were greater than 73%. This method proved to be simple, reproducible and feasible for pharmacokinetic studies of glucosamine sulfate in healthy volunteers after a single oral administration (1500 mg). The pharmacokinetic parameters and relative bioavailabilities were investigated for both domestic glucosamine sulfate tablet and capsule preparations compared with an imported capsule product.

Optimizing high‐performance liquid chromatography method for quantification of glucosamine using 6‐aminoquinolyl‐N‐hydroxysuccinimidyl carbamate derivatization in rat plasma: application to a pharmacokinetic study

“…This method greatly improved the sensitivity with LOD of 30 ng/mL compared with other derivative methods. The LOD was comparable to those of LC-MS reported by Tao-min Huang (Huang et al, 2006b) and satisfactory precision and accuracy were also obtained. The results indicated that this method could exactly quantitate glucosamine in plasma and was suitable for pharmacokinetic studies, and even might also be suitable for pharmacokinetic studies of other compounds containing amino group.…”

“…However, these results still showed a relatively lower limit of quantitation (LOQ) and sensitivity. Further, liquid chromatography with electrospray ionization mass spectrometry (LC-ESI-MS) was also developed for the assay of GlcN in biological sample (Huang et al, 2006b) with a satisfactory linear range of 0.1-20 μg/mL. However, the costly apparatus prevented it from becoming a routine technique.…”

Fast assay of glucosamine in pharmaceuticals and nutraceuticals by capillary zone electrophoresis with contactless conductivity detection

“…formulations while being slightly better than in previous HPLC or CE assays using spectrophotometric detection [5,16]. Nevertheless, it is not usable for the assay of GlAm in biological fluids where high-sensitivity MS, fluorescence, or LIF detection after derivatization (with typical LODs around 5-35 ng/mL of GlAm) is required [7,10,11,13,14]. The results of run-to-run repeatability of migration times and peak area ratios for two concentration levels of GlAm and K 1 in standard solutions are shown in Table 2.…”

“…For the HPLC assay of GlAM in body fluids, sensitive detection is desirable and therefore MS [9][10][11], pulsed amperometric detection [12] and fluorimetric detection [13,14] of derivatized GlAm are methods of choice. HPLC assays with refractometric detection [15] or UV detection at 195 nm [16] were devised for the quality control of nutraceuticals containing GlAm.…”

Determination of Glucosamine in Human Plasma by High-Performance Liquid Chromatography-Atmospheric Pressure Chemical Ionization Source-Tandem Mass Spectrometry

“…Both safety trials and toxicology studies show that glucosamine has a large safe dose range [7,[16][17][18][19]. There are few articles about the determination methods for glucosamine [20][21][22][23]. In this study, a sensitive, specific and rapid high-performance liquid chromatography-atmospheric pressure chemical ionization source-tandem mass spectrometric (HPLC-APCI-MS/MS) method is developed and validated, which has never been used for the determination of glucosamine in human plasma.…”